CN100418622C - A novel solid-phase micro-extraction head with polythiophene and preparation method thereof - Google Patents
A novel solid-phase micro-extraction head with polythiophene and preparation method thereof Download PDFInfo
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- CN100418622C CN100418622C CNB2006100391443A CN200610039144A CN100418622C CN 100418622 C CN100418622 C CN 100418622C CN B2006100391443 A CNB2006100391443 A CN B2006100391443A CN 200610039144 A CN200610039144 A CN 200610039144A CN 100418622 C CN100418622 C CN 100418622C
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- polythiophene
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Abstract
The present invention relates to a novel polythiophene solid phase micro extraction head and a preparation method thereof, which belongs to the technical field of environmental monitoring instruments. In the preparation method, metal wires are inserted into an injection device to form a simple solid phase micro extraction device; the front ends of the metal wires are used as work electrodes, and a triple electrode system is formed by combining platinum sheet pair electrodes and saturated calomel reference electrodes; the triple electrode system is put in an anhyrous BF3 ether solution containing thiophene; polythiophene coating layers sticking to the surfaces of the front ends of the metal wires are formed by using an electrochemical method; redistilled water and methanol solution are used for washing, and thus, the novel solid phase micro extraction head is prepared. The prepared solid phase micro extraction head has favorable selectivity on extracting polar, non-polar, volatile and nonvolatile trace organic pollutants. Compared with commercial coating layers, the polyaniline coating layers have the advantages of high physical and chemical stability and long service life. The extraction head is suitable for analyzing various kinds of organic matter in complicated samples, and has favorable application potential in fields of environmental monitoring, food sanitation, inspection and quarantine, etc.
Description
One, technical field
The present invention relates to a kind of solid-phase micro-extraction head with polythiophene that is applied to multiple environmental pollutant analysis and preparation method thereof.
Two, background technology
Solid phase micro-extraction technique (SPME) is a kind of novel sample pre-separation beneficiation technologies, it need not solvent, fast, convenient, fat-soluble organic matter had higher selectivity and stronger accumulation ability, be specially adapted to the analysis of trace materials, become the strong means of lasting organic pollution rapid analysis monitoring in the water body.SPME has been applied to many fields at present, as agricultural chemicals, phenols, Polychlorinated biphenyls, polycyclic aromatic hydrocarbon (PAHs) etc. are carried out analyzing and testing.
But, the merchant sells in the SPME structure polymeric coating layer (as: dimethyl silicone polymer (PDMS) and polyacrylate (PA) etc.) of appendix on quartz fibre, and device predisposes to damage, non-refractory, the life-span lacks and cost an arm and a leg, and is difficult to promote the use of in common lab.
Polythiophene is a kind of conducting polymer, has big conjugation ∏-∏ structure, therefore has very strong heat endurance and anti-organic solvent.In addition, dense grain structure and big specific area, this has also determined it that bigger adsorption capacity and fast extraction equilibrium are arranged.
By document retrieval, find no and close the relevant document that polythiophene is used for solid phase micro-extraction technique.
Three, summary of the invention
1. goal of the invention: the purpose of this invention is to provide a kind of solid-phase micro-extraction head with polythiophene that can be widely used in various organic pollutant analysis in the environment and preparation method thereof.
2. technical scheme:
Technical scheme of the present invention is:
A kind of preparation method of solid-phase micro-extraction head with polythiophene, it may further comprise the steps:
(1) wire is inserted in the injection device, make it form simple and easy solid-phase micro-extracting device;
(2) make the work electrode with front end of wire, to electrode, saturated calomel reference electrode is formed three-electrode system, puts into the anhydrous BF that contains thiophene in conjunction with platinized platinum
1In the diethyl ether solution;
(3) adopt potential sweep method, potentiostatic method, galvanostatic method or impulse polarization method to form the polythiophene coating that adheres to the front end of wire surface;
(4) with redistilled water and methanol solution washing, promptly make solid-phase micro-extraction head with polythiophene.
Wire in the step of the present invention (1) is convenient to later sampling and is got final product as long as hardness can satisfy in the insertion injection device, uses diameter: 0.1～0.5mm usually, length: the wire of 0.5～1.5cm, commonly used is stainless steel wire, low price and be easy to obtain.The anhydrous BF that contains thiophene in the step (2)
3Diethyl ether solution does not have specific (special) requirements, and what emphasize is to answer moisture-free or the moisture that contains few as far as possible in the solution.All effect preferably can be arranged when the concentration of thiophene is 0.05～0.5 mol, according to test, the thiophene concentration of suggestion is 0.1～0.2 mol.
Of the present inventionly also provide a kind of solid-phase micro-extraction head with polythiophene, comprise injection device and wire, there is the polythiophene coating on the front end of wire surface.
This solid phase micro-extracting head is prepared from according to above-described method.
This solid phase micro-extracting head is first use before in the gas-chromatography vaporizer 200～280 ℃, the aging 2～3h that heats up occurs up to the free from admixture peak.
Principle of the present invention:
According to thiophene " electropolymerization principle ", adopt electrochemical process, with the polythiophene electropolymerization on wire, to form the polythiophene coating.
The main method that is used for the synthetic polythiophene of electrochemistry at present is except above-mentioned electrokinetic potential scanning method, also have potentiostatic method, galvanostatic method, impulse polarization method and plasma polymerization method and true control steaming method etc., they generally all be thiophene in the solvent that proton is had inertia (acetonitrile, benzonitrile, nitrobenzene, BFEE, propene carbonate etc.), and contain strong acid anion (as ClO
4 -, PF
6 -, BF
4 -And AsF
6 -) and Li
+Or the existence of the electrolyte of tetraalkylammonium cation is down, electrochemical preparation generation polythiophene. on anode, carry out polymerization.Experiment shows that it is similar that these methods can make character within a short period of time, and bulk density is big, uniform particles, regular and polythiophene film that chemical property is stable.The thickness of film generally thickens along with the prolongation of polymerization time, and the thick more extraction quantity to organic micro-pollutant of polythiophene film is just big more, but the extraction time can prolong, in addition, peripheral pinhole diameter has also limited it can not be too thick.Electrode material, electrode potential, electrolyte solution kind all have certain influence to the polymerization of thiophene.So will following according to concrete experiment condition, concrete condition determines.
3. beneficial effect:
The characteristics of this method be polythiophene be direct electropolymerization on wire, in the process of electropolymerization, be by chemical bonding between the organic and inorganic phase (being solid phase coating and wire surface), so higher physical stability is arranged than commercial quartz fibre post.Aspect the life-span, discover to need only suitable operation that hundreds of times repeated uses and long the placement can not change its effect of extracting.Aspect pollutant analysis, no matter be polarity, nonpolar, volatility and all available polythiophene of difficult volatile organic pollution are analyzed, and this has broken the restriction of the conventional similar principle that mixes.The present invention is simple in structure, be easy to make, and has a extensive future.
Four, Figure of description
Structural representation when Fig. 1 uses for a kind of solid-phase micro-extraction head with polythiophene of the present invention;
Fig. 2 is the poly-coating sem photograph of solid-phase micro-extraction head with polythiophene of the present invention (A:100 a times, B:500 times, C:2000 doubly);
Fig. 3 is for using solid-phase micro-extraction head with polythiophene SPME organic chlorine agriculture chemicals gas chromatogram of the present invention.
Five, embodiment
With diameter is 0.35 millimeter wire 11, inserts in the injection device 12, makes it form easy solid-phase micro-extracting device, makes the work electrode with wire one end, and to electrode, saturated calomel reference electrode is formed three-electrode system in conjunction with platinized platinum.Put into then and contain 0.1mol 1
-1The anhydrous BF of thiophene
3In the diethyl ether solution, in the 1V scope, 50mV s
-1Under the condition, circulation 50～60 number of turns obtain polythiophene (PTh) coating 13 of dark red.Use redistilled water and methanol solution Washing 1～2 minute at last, promptly make polythiophene coating extracting head.This solid phase micro-extracting head is first use before in the gas-chromatography vaporizer 200～280 ℃, the aging 2～3h that heats up occurs up to the free from admixture peak.
Embodiment 2
With diameter is 0.25 millimeter wire 11, inserts in the injection device 12, makes it form easy solid-phase micro-extracting device, makes the work electrode with wire one end, and to electrode, saturated calomel reference electrode is formed three-electrode system in conjunction with platinized platinum.Put into then and contain 0.05mol 1
-1The anhydrous BF of thiophene
3In the diethyl ether solution, in the 0.6V scope, 40mV s
-1Under the condition, circulation 40～50 number of turns obtain polythiophene (PTh) coating 13 of dark red.Use redistilled water and methanol solution Washing 1～2 minute at last, promptly make polythiophene coating extracting head.This solid phase micro-extracting head is first use before in the gas-chromatography vaporizer 200～280 ℃, the aging 2～3h that heats up occurs up to the free from admixture peak.
Embodiment 3
With diameter is 0.45 millimeter wire, inserts in the injection device, makes it form easy solid-phase micro-extracting device, makes the work electrode with wire one end, and to electrode, saturated calomel reference electrode is formed three-electrode system in conjunction with platinized platinum.This three-electrode system put into contain 0.5mol 1
-1The anhydrous BF of thiophene
3In the diethyl ether solution, in the 1.6V scope, 60mV s
-1Under the condition, circulation 90～100 number of turns obtain polythiophene (PTh) coating 13 of dark red.Use redistilled water and methanol solution Washing 1～2 minute at last, promptly make polythiophene coating extracting head.This solid phase micro-extracting head is first use before in the gas-chromatography vaporizer 200～280 ℃, the aging 2～3h that heats up occurs up to the free from admixture peak.
Embodiment 4:
Basic operation is with embodiment 1, be diameter wiry be 0.1 millimeter, put into then and contain 0.1mol 1
-1The anhydrous BF of thiophene
3In the diethyl ether solution, in the 1V scope, 30mV s
-1Under the condition, 20 number of turns that circulate obtain polythiophene (PTh) coating 13 of dark red.All the other processing are all identical.
Embodiment 5:
Adopt the synthetic polythiophene coating of potentiostatic method, solvent is a kind of in acetonitrile, benzonitrile, nitrobenzene, BFEE, the propene carbonate, wherein contains strong acid anion (as ClO
4 -, PF
6 -, BF
4 -And AsF
6 -), at Li
+Or the existence of the electrolyte of tetraalkylammonium cation down, can prepare the coating that generates polythiophene.
Embodiment 6:
Adopt the synthetic polythiophene coating of galvanostatic method, solvent is a kind of in acetonitrile, benzonitrile, nitrobenzene, BFEE, the propene carbonate, wherein contains strong acid anion (as ClO
4 -, PF
6 -, BF
4 -And AsF
6 -), at Li
+Or the existence of the electrolyte of tetraalkylammonium cation down, can prepare the coating that generates polythiophene.
Embodiment 7:
Adopt the synthetic polythiophene coating of potential polarization method, solvent is a kind of in acetonitrile, benzonitrile, nitrobenzene, BFEE, the propene carbonate, wherein contains strong acid anion (as ClO
4 -, PF
6 -, BF
4 -And AsF
6 -), at Li
+Or the existence of the electrolyte of tetraalkylammonium cation down, can prepare the coating that generates polythiophene.
Embodiment 8:
(concentration is 200ppt to the polythiophene coating, (1) α-BHC to 15 kinds of organo-chlorine pesticides; (2) β-BHC; (3) γ-BHC; (4) δ-BHC; (5) HC; (6) Aldrin; (7) HE; (8) α-Endosulfan; (9) p, p ' DDE; (10) Dieldrin; (11) β-Endosulfan; (12) p, p '-DDD; (13) Endrin aldehyde; (14) Endosulfan sulfate.) effect of extracting such as Fig. 3.The result shows that this extracting head has good effect of extracting, and detectability reaches the ppt level, and reappearance is fine.
GC/ECD operating condition: DB-17 capillary quartz column (30m * 250 μ m * 0.25 μ m), heating schedule: 60 ℃ keep 0min, rise to 170 ℃ with 25 ℃/min, 4 ℃/min rises to 190 ℃, 8 ℃/min rises to 230 ℃, keeps 4min, and 1 ℃/min rises to 240 ℃, 25 ℃/min rises to 260 ℃, keeps 7min.Injector temperature: 260 ℃, detector temperature: 320 ℃.Nitrogen: 11.79psi.
Embodiment 9:
8 kinds of nitrobenzene compounds of polythiophene coating extraction, the gas chromatogram after the parsing shows: this coating has good selectivity, and detectability reaches the ppt level, and reappearance is fine.
The GC/ECD operating condition: DB-17 capillary quartz column (30m * 250 μ m * 0.25 μ m), heating schedule: 60 ℃ keep 0min, rise to 100 ℃ with 10 ℃/min, keep 6min, 8 ℃/min rises to 160 ℃, and 3 ℃/min rises to 200 ℃, 10 ℃/min rises to 250 ℃, keeps 2min.Injector temperature: 250 ℃, detector temperature: 300 ℃.Nitrogen: 14.33psi.
Embodiment 10:
The polythiophene coating is to the extraction of 6 kinds of pyrethrin pesticides (concentration is 5ppb).The result shows that this head has good effect of extracting, and detectability reaches the ppt level, and reappearance is fine.
The GC/ECD operating condition: DB-17 capillary quartz column (30m * 250 μ m * 0.25 μ m), heating schedule: 80 ℃ keep 0min, rise to 200 ℃ with 30 ℃/min, and 4 ℃/min rises to 260 ℃, and 0.5 ℃/min rises to 280 ℃, keep 5min.Injector temperature: 260 ℃, detector temperature: 320 ℃.Nitrogen: 12.7psi.
Claims (6)
1. the preparation method of a solid-phase micro-extraction head with polythiophene is characterized in that may further comprise the steps:
(1) wire is inserted in the injection device, make it form simple and easy solid-phase micro-extracting device;
(2) make the work electrode with front end of wire, to electrode, saturated calomel reference electrode is formed three-electrode system, puts into the anhydrous BF that contains thiophene in conjunction with platinized platinum
3In the diethyl ether solution;
(3) adopt potential sweep method, potentiostatic method, galvanostatic method or impulse polarization method to form the polythiophene coating that adheres to the front end of wire surface;
(4) with redistilled water and methanol solution washing, promptly make solid-phase micro-extraction head with polythiophene.
2. the preparation method of a kind of solid-phase micro-extraction head with polythiophene according to claim 1 is characterized in that the wire described in the step (1) is a stainless steel wire.
3. the preparation method of a kind of solid-phase micro-extraction head with polythiophene according to claim 1 and 2 is characterized in that containing in the step (2) the anhydrous BF of thiophene
3The thiophene concentration of diethyl ether solution is 0.1～0.2 mol.
4. the preparation method of a kind of solid-phase micro-extraction head with polythiophene according to claim 1 and 2 is characterized in that adopting potential sweep method in the step (3), and condition of work is: 0.6～1.6V, 40～60mVs
-1
5. a solid-phase micro-extraction head with polythiophene comprises injection device and wire, it is characterized in that the front end of wire surface is the polythiophene coating.
6. a kind of solid-phase micro-extraction head with polythiophene according to claim 5 is characterized in that making according to claim 1 or 2 described preparation methods.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2006100391443A CN100418622C (en) | 2006-03-28 | 2006-03-28 | A novel solid-phase micro-extraction head with polythiophene and preparation method thereof |
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| CN100418622C true CN100418622C (en) | 2008-09-17 |
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| CN115944948A (en) * | 2022-12-15 | 2023-04-11 | 大连工业大学 | Extraction head for realizing synchronous extraction of volatile and semi/non-volatile substances, integrated solid-phase micro-extraction method and application |
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| US6905031B1 (en) * | 1999-09-13 | 2005-06-14 | The Regents Of The University Of California | Solid phase microextraction device using aerogel |
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| JPH08261999A (en) * | 1995-02-28 | 1996-10-11 | Mallinckrodt Baker Inc | Solid-phase micro-extraction,wherein trace amount of organicbody under test is improved |
| US6905031B1 (en) * | 1999-09-13 | 2005-06-14 | The Regents Of The University Of California | Solid phase microextraction device using aerogel |
| CN1417580A (en) * | 2002-12-04 | 2003-05-14 | 中国科学院生态环境研究中心 | Prepn of polyaniline coating for new-type solid microextracting head |
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