CN101468306A - Titanium-containing solid phase micro-extraction head and preparation method thereof - Google Patents
Titanium-containing solid phase micro-extraction head and preparation method thereof Download PDFInfo
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- CN101468306A CN101468306A CNA2007103085124A CN200710308512A CN101468306A CN 101468306 A CN101468306 A CN 101468306A CN A2007103085124 A CNA2007103085124 A CN A2007103085124A CN 200710308512 A CN200710308512 A CN 200710308512A CN 101468306 A CN101468306 A CN 101468306A
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- extracting head
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Abstract
The invention provides a solid phase micro-extracting head. An extracting head fiber of the solid phase micro-extracting head is made of titanium or titanium alloy, and the surface of the extracting head fiber is provided with a titanium dioxide coating which can be a nano titanium dioxide coating. The extracting head specifically consists of a plastic screw head (1), a titanium wire (2), a rubber gasket (3), a metal supporting body (4) and an outer stainless steel tube (5), wherein the titanium wire (2) is the extracting head fiber. The mechanical property of the solid phase micro-extracting head which is not easy to break is increased, wherein TiO2, in particular a TiO2 nano material has good stability and strong adsorptive capacity, and further improves operation efficiency and analysis accuracy of solid phase micro-extracting. A preparation method for the solid phase micro-extracting head has the advantages of low cost, good product firmness, easy preparation, good preparation reproducibility, and the like.
Description
Technical field
The present invention relates to a kind of extracting head and preparation method thereof, particularly a kind of solid phase micro-extracting head and preparation method thereof.
Background technology
The structure of existing solid phase micro-extracting head comprises extracting head body and extracting head fiber 6 as shown in Figure 1, and described extracting head body is by plastics screw terminal 1, interior stainless steel tube 2, rubber gasket 3, metal supporting body 4, outer stainless steel tube 5 is formed, and described extracting head fiber 6 surfaces have the extraction coating.
Because vitreous silica has good heat endurance and chemical stability, so it is that the optical fiber of material is as the extracting head fiber that present commercial extracting head is all selected with it, at its surface-coated the mutually fixing of enrichment and analysis that be used for, but because the vitreous silica fiber fractures easily, so people also consider to adopt other material preparation extracting head fiber, to improve service life.
Metal has good mechanical performance, and is also high temperature resistant, is the desirable extracting head fiber material of a class.Liu etc. are fixed on the porous silicon of 100 μ m and are used for extraction (LiuY on the stainless steel fibre by High temp. epoxy resins, Lee M L, Hageman K J, YangY, Hawthorne S B.SPME of PAHsfrom aqueous samples, using fibers coated with HPLC chemically bondedsilica stationary phases.Anal.Chem., 1997 (69): 5001-5005.).Olesik etc. are coated in low temperature glass carbon film on the stainless steel wire, this film can be high temperature resistant to 1000 ℃, experiment shows that it has selectivity preferably to polar molecule, and three kinds of smell substance (M.Ciardina in the water have successfully been detected, S.V.Olesik.Application of low temperature glassy carbon films in solid phasemicroextraction.Anal.Chem., 2001 (73): 5841-5851.).Farajzadeh etc. mix cellulose acetate and polyvinyl chloride, be coated with stain on filamentary silver, and with it as the solid phase micro-extracting head coating material, extracted the alkane (M.A.Farajzadeh in the water sample, M.Hatami.A new selectiveSPME fiber for some n-alkanes and its use for headspace sampling of aqueoussamples.J.Sep.Sci., 2003 (26): 802-808.).
Wire is soaked in the solution, obtains metallic compound by chemistry or electrochemical method and also can be used in the SPME.As Djozan etc. the copper wire of cleaning is soaked in the copper chloride solution, the copper wire surface can cover one deck cuprous chloride crystal, and this coating can be used to extract volatile amine substance, and detectability can reach 0.1-0.3ngmL
-1(D.Djozan, Y.Assadi, G.Karim-Nezhad.Modified copper wire as solid-phase microextraction fiber selective extractionof some amines.Chromatographia, 2002 (56): 611-616.).Also prepare the aluminium wire (D.Djozan of oxidation with similar method, Y.Assadi, S.H.Haddadi.Anodized aluminumwire as a solid phase microextraction fiber.Anal.Chem., 2001 (73): 4054-4058.), zinc silk (the D.Djozan that electrochemical oxidation is handled, L.Abdollahi.Anodizedzinic wire as a solid phase microextraction fiber.Chromatographia, 2003 (57): 799-804.) and copper wire (D.Djozan, M.Amir-Zehmi.Copper sulfide wire as aselective fiber in solid phase microextraction.Chromatographia, 2003 (58): 221-224.).
TiO
2Nano material is to use a more class nanometer oxide material at present, because its excellent absorption property and good stable, can be used as solid phase extraction adsorbents heavy metal ion is adsorbed (Vassileva E, Proinova I, Hadj iivanov K.Solid-phase extraction of heavymetal ions on a high surface area titanium dioxide (anatase) .Analyst, 1996121 (5): 607-612.).Also be applied to the DDT class agricultural chemicals in the enrichment water sample week etc., obtained good effect (Zhou Q, DingY, Xiao J, Liu G, Guo X.Investigation of thefeasibility of TiO
2Nanotubes for the enrichment of DDT and its metabolites attrace levels in environmental water samples.J.Chromatogr.A, 20071147:10-16.).But at present also not about TiO
2The report that nano material is used aspect SPME.
Summary of the invention
The objective of the invention is in order to overcome the defective of present commercialization extracting head, thereby a kind of firmer, low-cost, solid phase micro-extracting head of being easy to prepare is provided.
The extracting head fiber of solid phase micro-extracting head provided by the invention is made by titanium or titanium alloy, preferably is made of titanium.As shown in Figure 2, described extracting head is by plastics screw terminal (1), titanium silk (2), and rubber gasket (3), metal supporting body (4), outer stainless steel tube (5) is formed, and wherein titanium silk (2) is the extracting head fiber.
Described extracting head fiber surface can have coating of titanium dioxide, and this coating of titanium dioxide can be formed through oxidation by the extracting head fiber surface, is preferably formed by the titanium direct oxidation, and described direct oxidation is chemical reaction oxidation and/or electrochemical oxidation.Described coating of titanium dioxide is preferably nanometer titanium dioxide coating, for example titania nanotube or titania nanoparticles.
Another object of the present invention provides a kind of preparation method of solid phase micro-extracting head, and this method may further comprise the steps:
(1) the titanium silk after will cleaning places H
2O
2In carry out oxidation reaction, the reaction afterwash that finishes;
(2) solid phase micro-extracting head that above-mentioned titanium silk will be housed inserts the gas-chromatography injection port, and is aging under nitrogen protection.
In the preparation method of above-mentioned solid phase micro-extracting head, when described titanium silk cleans, soak materials such as the oxide remove titanium silk surface and greasy dirt with acid solution, dry behind the deionized water rinsing, wherein said acid solution consists of HF:HNO
3: H
2O=1:3:6; Titanium silk after the cleaning places H
2O
2In in 80 ℃ the reaction 1 day; Ageing time is 0.5-2 hour under the described nitrogen protection, and aging temperature is 250-350 ℃.
Compare with existing solid phase micro-extracting head, the present invention mainly contains following advantage:
1. easy fracture not.The present invention uses titanium or titanium alloy to replace quartz fibre in traditional solid phase micro-extracting head, has therefore increased the mechanical performance of extracting head; Also can utilize the memory effect of some titanium alloy, prepare unbending fiber.The titanium silk can directly form nano-TiO on its surface through chemical oxidation or electrochemical oxidation
2And make solid-phase micro-extraction fibre, avoided adsorbent is coated the trouble of quartz fibre surface preparation coating.
2. good stable and adsorption capacity by force.TiO
2, TiO particularly
2Nano material has good stable and strong adsorption capacity, and it is applied in the solid phase micro-extraction technique, can further improve the operating efficiency and the precision of analysis of SPME.
3. adsorbent coating (nano-TiO
2) generate at fiber (titanium silk) surface in situ, overcome the adhesions that preparation method commonly used caused such as the adsorbent coating being coated fiber surface not firm, easily come off and shortcoming such as crawling is even.
Compare with the preparation method of existing solid phase micro-extracting head, the present invention mainly contains following advantage:
1. low-cost.Inexpensive being easy to get such as titanium silk of the present invention, hydrogen peroxide and acid, on average the cost of each extracting head has only 20 yuan, compares for 700 yuan every with commercial PDMS extracting head, greatly reduces production cost;
2. fastness is good.Described titanium silk surface is through oxidation processes, and original position forms coating of titanium dioxide or nanometer titanium dioxide coating, and the nanometer titanium dioxide coating of in-situ oxidation preparation combines firmly long service life with titanium silk matrix;
3. be easy to preparation.Adopt method of the present invention, simple chemical reaction can be prepared high performance solid phase micro-extracting head, all can realize the prepared in batches of this extracting head in common laboratory;
4. preparation favorable reproducibility.By control reaction time and reaction temperature, can realize the good reproduction of extracting head preparation;
5. saving experimental period, the coating layer thickness of the present invention preparation have only several microns, can be very fast reach extraction equilibrium, obtaining the good reproducible experimental period of having saved simultaneously.
Description of drawings
Fig. 1 is former commercial solid phase micro-extracting head structure chart.
Fig. 2 is a solid phase micro-extracting head structure chart of the present invention.
The specific embodiment
Below in conjunction with embodiment, solid phase micro-extracting head of the present invention and preparation method thereof is described in further detail, but the invention is not restricted to this embodiment.
Fig. 2 has provided the structure chart of solid phase micro-extracting head of the present invention; wherein plastics screw terminal 1, titanium silk 2, rubber gasket 3, metal supporting body 4 and outer stainless steel tube 5 have constituted extracting head jointly; plastics screw terminal 1 is installed in the upper end of titanium silk 2; the outside that outer stainless steel tube 5 is enclosed within titanium silk 2 plays a protective role; and outer stainless steel tube upper end is provided with metal supporting body 4, and described metal supporting body 4 is provided with rubber gasket 3.Select the titanium silk of the about 0.28mm of diameter in the present embodiment for use, its surface forms the layer of titanium dioxide nano material through oxidation, and described titanium dioxide layer thickness is 2 μ m.
Extracting head preparation method's concrete steps of present embodiment are as follows:
The titanium silk cleans earlier, and concrete operations are that the titanium silk is placed acid solution (HF:HNO
3: H
2O=1:3:6) soaked two minutes in, take out then and place deionized water for ultrasonic cleaning three times, taking-up is dried;
Titanium silk after cleaning is placed H
2O
2In in 80 ℃ the reaction 1 day, water is rinsed well then;
With above-mentioned titanium silk with coating and the plastics screw terminal 1 that obtains, rubber gasket 3, metal supporting body 4, outer stainless steel tube 5 is assembled into solid phase micro-extracting head;
The solid phase micro-extracting head that the titanium silk is housed is inserted the gas-chromatography injection port, wore out 1 hour under nitrogen protection, aging temperature is 280 ℃, promptly can be used for SPME.
The above-mentioned titanium dioxide extracting head that makes is applied to extract organo-chlorine pesticide in the water sample, has good stability, its relative standard deviation is 3.2-3.0% (five replication).In addition, utilize the solid phase micro-extracting head of present embodiment also to measure the content of organo-chlorine pesticide in the environmental water sample, reclaim by mark-on, the rate of recovery all reaches the requirement of conventional analysis, illustrates that this extracting head can be applied to the mensuration in the actual sample.
Claims (14)
1. a solid phase micro-extracting head is characterized in that, the extracting head fiber of this solid phase micro-extracting head is made by titanium or titanium alloy.
2. according to the described solid phase micro-extracting head of claim 1, it is characterized in that described extracting head fiber is made of titanium.
3. according to claim 1 or 2 described solid phase micro-extracting heads, it is characterized in that described extracting head is by plastics screw terminal (1), titanium silk (2), rubber gasket (3), metal supporting body (4), outer stainless steel tube (5) is formed.
4. according to each described solid phase micro-extracting head in the claim 1 to 3, it is characterized in that described extracting head fiber surface has coating of titanium dioxide.
5. according to each described solid phase micro-extracting head in the claim 1 to 4, it is characterized in that described coating of titanium dioxide is a nanometer titanium dioxide coating.
6. according to each described solid phase micro-extracting head in the claim 1 to 5, it is characterized in that described nanometer titanium dioxide coating is titania nanotube or titania nanoparticles.
7. according to each described solid phase micro-extracting head in the claim 1 to 6, it is characterized in that described extracting head fiber surface forms coating of titanium dioxide through oxidation.
8. according to each described solid phase micro-extracting head in the claim 1 to 7, it is characterized in that described coating of titanium dioxide is formed by the titanium direct oxidation.
9. according to each described solid phase micro-extracting head in the claim 1 to 8, it is characterized in that described direct oxidation is chemical reaction oxidation and/or electrochemical oxidation.
10. the preparation method of a solid phase micro-extracting head is characterized in that, may further comprise the steps:
(1) the titanium silk after will cleaning places H
2O
2In carry out oxidation reaction, the reaction afterwash that finishes;
(2) solid phase micro-extracting head that described titanium silk will be housed inserts the gas-chromatography injection port, and is aging under nitrogen protection.
11. the preparation method according to the described solid phase micro-extracting head of claim 10 is characterized in that, when described titanium silk cleans, soaks materials such as the oxide remove titanium silk surface and greasy dirt with acid solution, dries behind the deionized water rinsing.
12. the preparation method according to the described solid phase micro-extracting head of claim 11 is characterized in that, described acid solution consists of HF:HNO
3: H
2O=1:3:6.
13. the preparation method according to the described solid phase micro-extracting head of claim 10 is characterized in that, the titanium silk after the described cleaning places H
2O
2In in 80 ℃ the reaction 1 day.
14. the preparation method according to the described solid phase micro-extracting head of claim 10 is characterized in that, ageing time is 0.5-2 hour under the described nitrogen protection, and aging temperature is 250-350 ℃.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102636595A (en) * | 2012-04-13 | 2012-08-15 | 延边大学 | Continuous gas in-tube solid phase microextraction device combined with gas chromatography for use |
| CN103127919A (en) * | 2013-03-19 | 2013-06-05 | 北京师范大学 | Method for preparing titanium-based graphene coating for solid phase microextraction |
| CN104084054A (en) * | 2014-06-18 | 2014-10-08 | 南京理工大学 | Preparation method for supported ordered mesoporous carbon film used for solid phase microextraction |
| CN105582893A (en) * | 2015-12-17 | 2016-05-18 | 中国科学院生态环境研究中心 | Solid phase microextraction head based on ionic liquid coating and preparation method thereof |
| CN105709457A (en) * | 2014-12-05 | 2016-06-29 | 中国科学院大连化学物理研究所 | Solid-phase extraction device and application thereof |
| CN109173983A (en) * | 2018-08-07 | 2019-01-11 | 济南大学 | A method of hybridization of ionic liquid aerosil coating solid phase micro-extraction fiber is prepared in situ |
| CN115248204A (en) * | 2022-07-20 | 2022-10-28 | 济南大学 | Titanium dioxide solid-phase microextraction probe for Raman detection and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102636595A (en) * | 2012-04-13 | 2012-08-15 | 延边大学 | Continuous gas in-tube solid phase microextraction device combined with gas chromatography for use |
| CN103127919A (en) * | 2013-03-19 | 2013-06-05 | 北京师范大学 | Method for preparing titanium-based graphene coating for solid phase microextraction |
| CN104084054A (en) * | 2014-06-18 | 2014-10-08 | 南京理工大学 | Preparation method for supported ordered mesoporous carbon film used for solid phase microextraction |
| CN105709457A (en) * | 2014-12-05 | 2016-06-29 | 中国科学院大连化学物理研究所 | Solid-phase extraction device and application thereof |
| CN105582893A (en) * | 2015-12-17 | 2016-05-18 | 中国科学院生态环境研究中心 | Solid phase microextraction head based on ionic liquid coating and preparation method thereof |
| CN105582893B (en) * | 2015-12-17 | 2018-03-06 | 中国科学院生态环境研究中心 | A kind of solid phase micro-extracting head based on ionic liquid coating and preparation method thereof |
| CN109173983A (en) * | 2018-08-07 | 2019-01-11 | 济南大学 | A method of hybridization of ionic liquid aerosil coating solid phase micro-extraction fiber is prepared in situ |
| CN115248204A (en) * | 2022-07-20 | 2022-10-28 | 济南大学 | Titanium dioxide solid-phase microextraction probe for Raman detection and preparation method thereof |
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Open date: 20090701 |