CN101530679A - Solid phase micro-extraction stainless steel fiber and preparation method thereof - Google Patents
Solid phase micro-extraction stainless steel fiber and preparation method thereof Download PDFInfo
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- CN101530679A CN101530679A CN200910067962A CN200910067962A CN101530679A CN 101530679 A CN101530679 A CN 101530679A CN 200910067962 A CN200910067962 A CN 200910067962A CN 200910067962 A CN200910067962 A CN 200910067962A CN 101530679 A CN101530679 A CN 101530679A
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Abstract
The invention relates to a novel solid phase micro-extraction stainless steel fiber and a preparation method thereof, which provides a method for easily and rapidly preparing the solid phase micro-extraction stainless steel fiber with high stability and high reproducibility. The preparation method is as follows: soaking the part of cleaned stainless steel wire into acid for treatment; washing by water; ageing under the protection of nitrogen, obtaining the solid phase micro-extraction stainless steel fiber; mounting the prepared solid phase micro-extraction stainless steel fiber in a microliter syringe, obtaining a simple solid phase micro-extraction device. The method is simple in operation and low in cost. The prepared solid phase micro-extraction stainless steel fiber has excellent extraction performance on all trace amount organic pollutants. Compared with commercial solid phase micro-extraction device, the solid phase micro-extraction device has better mechanical strength and thermal stability, and has low cost and long service life. The extraction fiber has excellent application potential in fields of environmental monitoring, food hygiene and the like.
Description
[technical field]:
The present invention relates to a kind of novel solid phase micro extraction fiber and preparation method thereof.
[background technology]:
Merged into one sampling, extraction and sample treatment by the solid phase micro-extraction technique that Pawliszyn proposes the nineties in 20 century.This method is simple, flexibly, cost is low, solvent-free, fast and very sensitive.
At present, commercial solid-phase micro-extraction fibre mainly is to be carrier with the quartz.Coating mainly contains, dimethyl silicone polymer (PDMS), polyacrylate (PA), dimethyl silicone polymer/divinylbenzene (PDMS/DVB), polyethylene glycol/divinylbenzene (PEG/DVB), Carboxen/PDMS, Carbowax/ divinylbenzene (CW/DVB) and polyacrylonitrile (PAN).These coatings all are the surfaces that is fixed on quartz fibre by the method for physics or chemistry.
Commercial extracting fiber has demonstrated a series of defective: fiber easy fracture, thermally labile (common 240～280 ℃), the easy bending of fiber, coating easily comes off and cost an arm and a leg.Therefore, preparation solid-phase micro-extraction fibre simple, durable, cheap, high sensitivity more and more obtains people's attention.
In order to overcome these shortcomings, some researchers adopt different wires to replace quartz fibre, to strengthen the mechanical strength of extracting head.Hou etc. on stainless steel wire with epoxide-resin glue with C
16-MCM-41 be stained with (Talanta, 2004,62,241-246); Musteata etc. PAN is coated on the stainless steel wire (Anal.Chem.2007,79,6903-6911).For the heat endurance of fortifying fibre, Chong etc. successfully sol-gel technique is applied in the preparation of solid-phase micro-extraction fibre coating (Anal.Chem.1997,69,3889-3898).Simultaneously, people have proposed to utilize inorganic material as the solid-phase micro-extraction fibre coating again.One piece of article that Djozan etc. delivered in calendar year 2001 be exactly an example (Anal.Chem.2001,73,4054-4058).In this piece article, solid-phase micro-extraction fibre is that the aluminium wire of aluminium oxide is formed by the surface, and it has shown good character: firm, cost is low, good stability, and preparation is simple; Yet this fiber only is suitable for the analysis of humidity less than 25% gas sample.
[summary of the invention]:
The objective of the invention is to overcome the shortcoming of above-mentioned commercialization extracting head, provide a kind of simple, low-cost, prepare the method for high stability and high reproducible solid phase micro-extraction stainless steel fiber fast.
A simple and easy solid-phase micro-extracting device (see figure 1) provided by the invention is made up of the solid phase micro-extraction stainless steel fiber of 5 μ l microsyringes and preparation.Described solid phase micro-extraction stainless steel fiber is the stainless steel wire of hydrofluoric acid corrosion.
The preparation method of solid phase micro-extraction stainless steel fiber provided by the invention comprises the steps:
The first, the container that will fill acid solution is put into water-bath constant temperature, and temperature is 25～40 ℃;
The second, the partial-length of stainless steel wire is suspended in carries out corrosion treatment in the acid solution, the processing time is 10～60min;
Three, the stainless steel wire that second step was corroded takes out, and carefully rinses out acid residual on the stainless steel wire with clear water;
Four, stainless steel wire burin-in process under nitrogen protection that the 3rd step was cleaned up obtains solid phase micro-extraction stainless steel fiber.
The described acid of the first step is the hydrofluoric acid of mass concentration 40%.
Described stainless steel wire is 304 stainless steel wires.
The 4th step temperature of described burin-in process is 280～320 ℃, and ageing time is 2～4h.
The specific operation process of the inventive method is as follows:
(1) water-bath is put in the draughty fume hood, is heated to 25～40 ℃ of constant temperature;
(2) in polytetrafluoroethylcontainer container, add hydrofluoric acid, put it into the interior constant temperature of water-bath in (1);
(3) be the upper end that 304 stainless steel wires of 300 μ m are vertically fixed on polytetrafluoroethylcontainer container in (2) with a diameter, about 3～6cm stainless steel wire immersed in the hydrofluoric acid, reaction 10～60min;
The stainless steel wire that (4) will corrode takes out, and carefully rinses out hydrofluoric acid residual on the stainless steel wire with clear water;
(5) stainless steel wire in (4) is inserted the gas phase injection port, 280～320 ℃ of aging 2～4h obtain solid phase micro-extraction stainless steel fiber under protection of nitrogen gas.
The solid phase micro-extraction stainless steel fiber for preparing is packed in the 5 μ l microsyringes, promptly make simple and easy solid-phase micro-extracting device.
Advantage of the present invention and good effect:
The present invention only adopts cheap stainless steel wire and hydrofluoric acid to prepare solid phase micro-extraction stainless steel fiber.This method is simple, quick, with low cost.Simultaneously, the stainless steel fibre of preparation is durable, can be with more than hundreds of times; Favorable reproducibility; The bioaccumulation efficiency height.
This method has been successfully applied to polycyclic aromatic hydrocarbon, alkane and hydrophobic derivatives thereof in the enrichment water, simultaneously, successfully is used for the preenrichment of benzene series thing in agricultural product BHC, DDT and the gas.Therefore, this method has the potentiality of application in environmental monitoring and food hygiene field.
[description of drawings]:
Fig. 1 is a kind of SPME easy device schematic diagram.Wherein, 1 is solid phase micro-extraction stainless steel fiber, and 2 is syringe, and 3 is nook closing member.
Fig. 2 is the chromatogram that PAHs obtains in the enrichment water.
Fig. 3 is four kinds of BHC of enrichment (α-BHC, β-BHC, δ-BHC, γ-BHC) and four kinds of DDT (p, p '-DDE, o, p '-DDT, p, p '-DDD, p, chromatograms of p '-DDT) obtain.
[specific embodiment]:
Below by several specific embodiments technical scheme of the present invention is further described.
Embodiment 1
(a) water-bath is put in the draughty fume hood, is heated to 40 ℃ of constant temperature;
(b) in polytetrafluoroethylcontainer container, add the hydrofluoric acid of mass concentration 40%, put it into the interior constant temperature of water-bath in (a);
(c) be the upper end that 304 stainless steel wires of 300 μ m are vertically fixed on polytetrafluoroethylcontainer container in (b) with a diameter, make in about 4cm stainless steel wire immersion hydrofluoric acid.Reaction 10～15min;
The stainless steel wire that (d) will corrode takes out, and carefully rinses out hydrofluoric acid residual on the stainless steel wire with clear water;
(e) stainless steel wire in (d) is inserted gas phase injection port 320 ℃ of aging 4h under protection of nitrogen gas, obtain solid phase micro-extraction stainless steel fiber.
With the solid phase micro-extraction stainless steel fiber 1 that the prepares (see figure 1) in the nook closing member 3 of 5 μ l microsyringes of packing into, promptly make simple and easy solid-phase micro-extracting device.
Embodiment 2
(a) water-bath is put in the draughty fume hood, is heated to 25 ℃ of constant temperature;
(b) in polytetrafluoroethylcontainer container, add the hydrofluoric acid of mass concentration 40%, put it into the interior constant temperature of water-bath in (a);
(c) be the upper end that 304 stainless steel wires of 300 μ m are vertically fixed on polytetrafluoroethylcontainer container in (b) with a diameter, make in about 4cm (or the random length among 3～6cm) stainless steel wire immersion hydrofluoric acid.React about 1h;
The stainless steel wire that (d) will corrode takes out, and carefully rinses out hydrofluoric acid residual on the stainless steel stainless steel wire with clear water;
(e) stainless steel wire in (d) is packed in the microsyringe, promptly make solid-phase micro-extracting device.The solid-phase micro-extraction fibre for preparing is inserted gas phase injection port 280 ℃ of aging 4h under protection of nitrogen gas.
Embodiment 3
The solid phase micro-extraction stainless steel fiber that embodiment 2 is made is used for measuring the preenrichment of water sample naphthalene, acenaphthene, fluorenes, phenanthrene, fluoranthene, six kinds of EPA-PAHs of pyrene and (sees accompanying drawing 2, each analyte concentration is 10ppb), obtain having improved 2630～3570 times before the remolding sensitivity enrichment of detection limit after the enrichment.Detect and be limited to 0.24～0.63ppb.Test repeatedly, its relative standard deviation is less than 6.0%.Concentration effect did not have to change substantially after this extracting fiber used 250 times.
The GC-FID operating condition: SE-54 capillary quartz column (30m * 0.53mm. * 1.0 μ m), heating schedule: 180 ℃ keep 1.5min, with 4 ℃ of min
-1Be warming up to 220 ℃, keep 5min.Injector temperature: 320 ℃, detector temperature: 320 ℃.
With the extracting fiber that makes be respectively applied for benzene in the head space enriched gas sample, toluene, ethylbenzene, (each analyte concentration is 5.0 to dimethylbenzene
Ppt) enrichment, detection limit reach the ppt level.And to the enrichment of n-hexane, normal octane, n-decane, n-undecane, n-dodecane
Efficient has improved hundreds of times, and detection limit reaches the ppb level.
The GC-FID operating condition: SE-54 capillary quartz column (30m * 0.53mm. * 1.0 μ m), the heating schedule when separate detecting the benzene series thing: from 50 ℃ with 5 ℃ of min
-1Be warming up to 100 ℃.Injector temperature: 280 ℃, detector temperature: 280 ℃.Separate the heating schedule when detecting linear paraffin: 50 ℃ keep 2min, 12 ℃ of min
-1Be warming up to 120 ℃.
Embodiment 5
The extracting fiber that makes is used for the agricultural product organo-chlorine pesticide (comprises four kinds of isomers of BHC and p, p '-DDE, o, p '-DDT, p, p '-DDD, p, the preenrichment (see accompanying drawing 3, the concentration of each analyte is 1ppb) of p '-DDT), detection limit reaches the ppt level.
GC-ECD operating condition: SE-54 capillary quartz column (15m * 0.53mm. * 1.0 μ m), 230 ℃ of constant temperature.Injector temperature: 280 ℃.Detector temperature: 280 ℃.
Claims (5)
1, a kind of solid phase micro-extraction stainless steel fiber is characterized in that this solid phase micro-extraction stainless steel fiber is directly corroded stainless steel wire by acid to obtain.
2, the preparation method of the described solid phase micro-extraction stainless steel fiber of a kind of claim 1 is characterized in that this method comprises the steps:
The first, the container that will fill acid solution is put into water-bath constant temperature, and temperature is 25～40 ℃;
The second, the partial-length of stainless steel wire is suspended in carries out corrosion treatment in the acid solution, the processing time is 10～60min;
Three, the stainless steel wire that second step was corroded takes out, and carefully rinses out acid residual on the stainless steel wire with clear water;
Four, stainless steel wire burin-in process under nitrogen protection that the 3rd step was cleaned up obtains solid phase micro-extraction stainless steel fiber.
3, preparation method according to claim 2 is characterized in that the described acid of the first step is the hydrofluoric acid of mass concentration 40%.
4,, it is characterized in that described stainless steel wire of second step is 304 stainless steel wires according to claim 2 or 3 described preparation methods.
5, according to claim 2 or 3 described preparation methods, it is characterized in that the temperature of described burin-in process of the 4th step is 280～320 ℃, ageing time is 2～4h.
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Cited By (8)
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| CN101942762A (en) * | 2010-09-29 | 2011-01-12 | 天津市春升清真食品有限公司 | Metal carrier solid phase micro-extraction fiber |
| CN101947437A (en) * | 2010-09-29 | 2011-01-19 | 天津市春升清真食品有限公司 | Solid-phase micro-extraction fiber with polymer coating and preparation method thereof |
| CN101972635A (en) * | 2010-09-29 | 2011-02-16 | 天津市春升清真食品有限公司 | Stir and extraction bar for polymer coating and preparation method thereof |
| CN102068962A (en) * | 2010-10-19 | 2011-05-25 | 天津春发食品配料有限公司 | Metal carrier solid-phase micro-extraction fiber and preparation method thereof |
| CN104771934A (en) * | 2014-12-31 | 2015-07-15 | 中国广州分析测试中心 | Solid phase micro-extraction apparatus |
| CN106835258A (en) * | 2016-12-15 | 2017-06-13 | 华北电力大学（保定） | A kind of dot matrix type etches the preparation method and applications of stainless steel fibre |
| CN108034055A (en) * | 2017-12-29 | 2018-05-15 | 中国烟草总公司郑州烟草研究院 | A kind of covalent organic framework solid-phase micro-extraction fibre and preparation method thereof |
| CN112295264A (en) * | 2020-11-30 | 2021-02-02 | 清华大学深圳国际研究生院 | Method for manufacturing solid phase micro-extraction probe |
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- 2009-02-27 CN CN2009100679628A patent/CN101530679B/en not_active Expired - Fee Related
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| CN101972635B (en) * | 2010-09-29 | 2012-11-21 | 天津市春升清真食品有限公司 | Preparation method of stir and extraction bar for polymer coating |
| CN101947437A (en) * | 2010-09-29 | 2011-01-19 | 天津市春升清真食品有限公司 | Solid-phase micro-extraction fiber with polymer coating and preparation method thereof |
| CN101972635A (en) * | 2010-09-29 | 2011-02-16 | 天津市春升清真食品有限公司 | Stir and extraction bar for polymer coating and preparation method thereof |
| CN101942762A (en) * | 2010-09-29 | 2011-01-12 | 天津市春升清真食品有限公司 | Metal carrier solid phase micro-extraction fiber |
| CN101947437B (en) * | 2010-09-29 | 2012-10-03 | 天津市春升清真食品有限公司 | Solid-phase micro-extraction fiber with polymer coating and preparation method thereof |
| CN102068962A (en) * | 2010-10-19 | 2011-05-25 | 天津春发食品配料有限公司 | Metal carrier solid-phase micro-extraction fiber and preparation method thereof |
| CN102068962B (en) * | 2010-10-19 | 2012-10-24 | 天津春发生物科技集团有限公司 | Preparation method of metal carrier solid-phase micro-extraction fiber |
| CN104771934A (en) * | 2014-12-31 | 2015-07-15 | 中国广州分析测试中心 | Solid phase micro-extraction apparatus |
| CN106835258A (en) * | 2016-12-15 | 2017-06-13 | 华北电力大学（保定） | A kind of dot matrix type etches the preparation method and applications of stainless steel fibre |
| CN106835258B (en) * | 2016-12-15 | 2019-03-08 | 华北电力大学（保定） | A kind of preparation method and applications of dot matrix type etching stainless steel fibre |
| CN108034055A (en) * | 2017-12-29 | 2018-05-15 | 中国烟草总公司郑州烟草研究院 | A kind of covalent organic framework solid-phase micro-extraction fibre and preparation method thereof |
| CN112295264A (en) * | 2020-11-30 | 2021-02-02 | 清华大学深圳国际研究生院 | Method for manufacturing solid phase micro-extraction probe |
| CN112295264B (en) * | 2020-11-30 | 2022-04-12 | 清华大学深圳国际研究生院 | Method for manufacturing solid phase micro-extraction probe |
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