CN101942762B - Preparation method of metal carrier solid phase micro-extraction fiber - Google Patents
Preparation method of metal carrier solid phase micro-extraction fiber Download PDFInfo
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- CN101942762B CN101942762B CN201010297216A CN201010297216A CN101942762B CN 101942762 B CN101942762 B CN 101942762B CN 201010297216 A CN201010297216 A CN 201010297216A CN 201010297216 A CN201010297216 A CN 201010297216A CN 101942762 B CN101942762 B CN 101942762B
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Abstract
The invention discloses a metal carrier solid phase micro-extraction fiber and relates to the field of trace analysis of organic matters in foods, environment and biological samples, which consists of a carrier and a coating on the surface of the carrier, wherein the carrier is a metal fiber with the length of 10-40mm and the diameter of 0.1-0.5mm, the coating comprises an absorbent layer, as well as a high-temperature resistant epoxy resin layer or an organic silicone resin layer; and the absorbent is aluminum oxide, titanium oxide, zirconium oxide or magnesium silicate. A coating material with good thermal stability and resistance to solvent washing can be formed through the metal carrier solid phase micro-extraction fiber, thereby realizing the enrichment of trace organic matters; the metal fiber is used for replacing the traditional quartz fiber to realize higher mechanical strength; the absorbent is combined on the metal fiber, thereby leading the absorbent to be convenient to carry out static headspace trapping on the samples; if r-Al2O3 with strong polarity is selected to be the absorbent, the metal carrier solid phase micro-extraction fiber is particularly applicable to enriching heterocyclic rings (including nitrogen, phosphorus and sulfur), aromatic hydrocarbons and organic amine.
Description
Technical field
The present invention relates to organic trace analysis field in food, environment, the biological sample, particularly a kind of metallic carrier solid-phase micro-extraction fibre.
Background technology
(solid phase microextraction, SPME) technology is a kind of sample pre-treatments technology of novelty in SPME.1989, the Belardi of Canadian Waterloo university and Pawliszynl reported first the SPME technology; 1993, the Supelco company of the U.S. released commercial SPME device; Nineteen ninety-five, Chen and Pawliszynl design SPME-high performance liquid chromatography (SPME-HPLC) combination interface device, and produce commodity by Supelco company.1997, Eisert and Pawliszyn designed interior (In-tube) SPME-HPLC combined apparatus of SPME-HPLC combined apparatus-pipe of auto injection; 1997, Nguyen etc. realized the on-line coupling of SPME-Capillary Electrophoresis (SPME-CE).In addition, SPME also can with Fourier transform infrared spectroscopy (FTIR), ultra-violet absorption spectrum (UV), inductivity coupled plasma mass spectrometry couplings such as (ICP-Ms).
SPME centralized procurement appearance, extraction, concentrate, sample introduction is in one, have easy, quick, portable, efficient, need not organic solvent and be easy to the advantage with analysis Instrument crosslinkings such as gas-chromatography, high performance liquid chromatography, gas chromatography mass spectrometry, Capillary Electrophoresis.Therefore, obtained in fields such as environmental analysis, food analysis, Pharmaceutical Analysis, biological sample analysises using widely.The evaluating objects thing of SPME also comprises inorganic matter, element etc. except organic matter, can be used for the analysis of all kinds of volatilizations and half volatile substance in the samples such as gas, liquid, solid.
Commercial the earliest SPME (Fiber SPME) device shape is made up of extracting head and handle two parts like a syringe.Extracting head is that a 1cm is long, scribbles the vitreous silica fiber of different fixing phase.Therefore, extracting head in use very easily fractures.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, a kind of metallic carrier solid-phase micro-extraction fibre is provided.
Technical scheme of the present invention is:
A kind of metallic carrier solid-phase micro-extraction fibre is made up of the coating of carrier and carrier surface, and said carrier is long 10-40mm, and diameter is the metal fibre of 0.1-0.5mm, and said coating comprises adsorbent layer, also comprises high-temperature-resistant epoxy resin layer or silicone resin layer; Said adsorbent is aluminium oxide, titanium oxide, zirconia or magnesium silicate.
A kind of metallic carrier solid-phase micro-extraction fibre, this extracting fiber are that the method according to following steps prepares:
(a), choose long 10-40mm, diameter is the metal fibre of 0.1-0.5mm, corrodes 10-60min with dense HF, takes out, and to neutral, uses N with distilled water flushing again
2Dry up;
(b), will pass through surface-coated one deck high-temperature-resistant epoxy resin of metal fibre or organic siliconresin that step (a) was handled, pick one deck adsorbent at skin again, coating or repeat to be coated with stain and pick and adjust coating layer thickness; Said adsorbent is aluminium oxide, titanium oxide, zirconia or magnesium silicate;
The extracting fiber that (c), will coat coating places and carries out hot setting in the baking oven;
(d), extracting fiber that hot setting is good, place in the middle of the cable type extractor according, with carrene in 40-80 ℃ of backflow 20-120min, to remove impurity.
Preferably, described metal fibre is stainless steel fibre or alloy fiber.
Preferably, described adsorbent is r-Al
2O
3Or titanium dioxide.
Preferably; The synthetic method of said high-temperature-resistant epoxy resin is stirred to dissolving fully in epoxy resin, adding organic solvent; Add curing agent, auxiliary agent and filler more successively; Stirring is uniformly dispersed each component, places below 5 ℃ to store for future use, and wherein the weight ratio of epoxy resin, curing agent, auxiliary agent and filler is 80-120: 10-80: 10-80: 10-60.
Preferably, said organic solvent is a kind of in xylene, toluene, benzene or the acetone.
Preferably, said auxiliary agent is a tertiary amine.
Preferably, said filler is a kind of in flake asbestos, aluminium powder or the titanium white powder.
Preferably, said curing agent is a pyromellitic dianhydride.
The coating layer thickness of the extracting fiber that the inventive method makes is 10-2000 μ m.
Advantage and good effect that the present invention has are:
The present invention utilizes synthetic high-temperature-resistant epoxy resin or organic siliconresin that adsorbent is fixed on the metal fibre surface, forms Heat stability is good, thereby the coating material of anti-solvent washing is realized the enrichment to trace organic substance.Replace traditional quartz fibre to make it have higher mechanical strength with metal fibre; Adsorbent is attached to the form on the metal fibre, is convenient to the static head space capture of adsorbent sample; If select r-Al
2O
3As adsorbent, it is strong polar adsorbent, is specially adapted to the enrichment to heterocycle (nitrogenous, phosphorus, sulfenyl), aromatic hydrocarbon, organic amine.
Description of drawings:
Fig. 1 is not for using the gas-chromatography baseline chart of extracting fiber;
Fig. 2 is for using the gas-chromatography baseline chart under the embodiment 1 extracting fiber desorption temperature;
Fig. 3 is the gas chromatogram that utilizes embodiment 1 extracting fiber extraction benzene series material;
Among Fig. 3, extracting substance is respectively benzene,toluene,xylene, chlorobenzene.
The specific embodiment
Comparison diagram 1 can draw with Fig. 2, under desorption temperature, can cause the loss of coating hardly.Fig. 3 is the gas chromatogram that utilizes benzene series material in the embodiment 1 extracting fiber extraction water, visible solid-phase micro-extraction fibre of the present invention to organic matter have the good adsorption performance and easy and simple to handle, save time, be particularly suitable for the analysis of trace, trace materials in the environment.
Embodiment 1
Choose long 20mm, diameter is the stainless steel fibre of 0.35mm, corrodes 30min with dense HF, takes out, and to neutral, uses N with distilled water flushing again
2Dry up; Take by weighing 100g epoxy resin, add xylene and be stirred to dissolving fully, add 15g pyromellitic dianhydride, 15g tertiary amine and 20g flake asbestos more successively, stirring is uniformly dispersed each component, makes high-temperature-resistant epoxy resin; At the surface-coated one deck high-temperature-resistant epoxy resin of the stainless steel fibre of handling, pick one deck r-Al at skin again
2O
3, place in the baking oven in 180 ℃ of hot setting 60min; The extracting fiber that hot setting is good places in the middle of the cable type extractor according, utilizes carrene in 60 ℃ of backflow 40min, makes the extracting fiber finished product.
Wherein epoxy resin is multifunctional glycidol type epoxy resin, and market is bought and obtained.
Embodiment 2
Choose long 20mm, diameter is the stainless steel fibre of 0.35mm, utilizes dense HF to corrode 20min, takes out, and to neutral, utilizes N with distilled water flushing
2Dry up; At the surface-coated one deck organic siliconresin of the stainless steel fibre of handling, pick layer of titanium dioxide at skin again, place in the baking oven in 180 ℃ of hot setting 60min.The extracting fiber that hot setting is good places in the middle of the cable type extractor according, with carrene in 60 ℃ of backflow 40min.Make the extracting fiber finished product.
Embodiment 3
Utilize the extracting fiber of making among the embodiment 1 that aldehydes matter in the water is analyzed, take the immersion mode to extract.
Embodiment 4
Utilize the extracting fiber of making among the embodiment 2 that perfume ingredient is fragrant and analyze, take the head space mode to extract.
Embodiment 5
Utilize the extracting fiber of making among the embodiment 1 that aniline category matter in pharmaceutical factory's waste water is detected, take the immersion mode to extract.
The above only is preferred embodiment of the present invention, is not technical scheme of the present invention is done any pro forma restriction.Every foundation technical spirit of the present invention all still belongs in the scope of technical scheme of the present invention any simple modification, equivalent variations and modification that above embodiment did.
Claims (7)
1. the preparation method of a metallic carrier solid-phase micro-extraction fibre; Coating by carrier and carrier surface is formed, and it is characterized in that: said carrier is long 10-40mm, and diameter is the metal fibre of 0.1-0.5mm; Said coating comprises adsorbent layer, also comprises the high-temperature-resistant epoxy resin layer; Said adsorbent is r-Al
2O
3This extracting fiber is that the method according to following steps prepares: (a), choose long 10-40mm, diameter is the metal fibre of 0.1-0.5mm, corrodes 10-60min with dense HF, takes out, and to neutral, uses N with distilled water flushing again
2Dry up; (b), will pass through the surface-coated one deck high-temperature-resistant epoxy resin of metal fibre that step (a) was handled, pick one deck r-Al at skin again
2O
3The extracting fiber that (c), will coat coating places and carries out hot setting in the baking oven; (d), extracting fiber that hot setting is good, place in the middle of the cable type extractor according, with carrene in 40-80 ℃ of backflow 20-120min, to remove impurity;
The synthetic method of said high-temperature-resistant epoxy resin is stirred to dissolving fully in epoxy resin, adding organic solvent; Add curing agent, auxiliary agent and filler more successively; Stirring is uniformly dispersed each component; Place below 5 ℃ to store for future use, wherein the weight ratio of epoxy resin, curing agent, auxiliary agent and filler is 80-120:10-80:10-80:10-60.
2. the preparation method of a kind of metallic carrier solid-phase micro-extraction fibre according to claim 1 is characterized in that: described metal fibre is an alloy fiber.
3. the preparation method of a kind of metallic carrier solid-phase micro-extraction fibre according to claim 2 is characterized in that: described metal fibre is a stainless steel fibre.
4. the preparation method of a kind of metallic carrier solid-phase micro-extraction fibre according to claim 1 is characterized in that: said organic solvent is a kind of in xylene, toluene, benzene or the acetone.
5. the preparation method of a kind of metallic carrier solid-phase micro-extraction fibre according to claim 1 is characterized in that: said auxiliary agent is a tertiary amine.
6. the preparation method of a kind of metallic carrier solid-phase micro-extraction fibre according to claim 1 is characterized in that: said filler is a kind of in flake asbestos, aluminium powder or the titanium white powder.
7. the preparation method of a kind of metallic carrier solid-phase micro-extraction fibre according to claim 1 is characterized in that: said curing agent is a pyromellitic dianhydride.
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| CN101942762B true CN101942762B (en) | 2012-10-10 |
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| CN105709457B (en) * | 2014-12-05 | 2018-01-09 | 中国科学院大连化学物理研究所 | A kind of solid-phase extraction device and its application |
| CN108034055B (en) * | 2017-12-29 | 2021-04-06 | 中国烟草总公司郑州烟草研究院 | Covalent organic framework solid phase micro-extraction fiber and preparation method thereof |
| CN110567786B (en) * | 2019-08-06 | 2020-09-29 | 中南大学 | Spatial resolution enrichment purification sampling method for mass spectrometry imaging |
| CN114345294B (en) * | 2022-01-10 | 2023-05-26 | 万华化学集团股份有限公司 | Zinc-manganese-zirconium modified mesoporous molecular sieve, preparation method and application |
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| WO2000017429A1 (en) * | 1998-09-21 | 2000-03-30 | University Of South Florida | Solid phase microextraction fiber structure and method of making |
| US6905031B1 (en) * | 1999-09-13 | 2005-06-14 | The Regents Of The University Of California | Solid phase microextraction device using aerogel |
| CN101468306A (en) * | 2007-12-29 | 2009-07-01 | 中国科学院生态环境研究中心 | Titanium-containing solid phase micro-extraction head and preparation method thereof |
| CN101239302B (en) * | 2008-03-11 | 2011-06-15 | 中山大学 | Extraction head of carbon nano-tube solid phase micro-extraction and preparation thereof |
| CN101530679B (en) * | 2009-02-27 | 2010-12-01 | 南开大学 | Solid phase micro-extraction stainless steel fiber and preparation method thereof |
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Non-Patent Citations (1)
| Title |
|---|
| 魏黎明等.r-Al2O3固相微萃取涂层的制备及其在水体和气态基质中的应用.《色谱》.2004,第22卷(第4期),第435-438页. * |
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