CN101209410A - Solid phase micro-extracting head and preparation thereof - Google Patents
Solid phase micro-extracting head and preparation thereof Download PDFInfo
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- CN101209410A CN101209410A CNA2006101715083A CN200610171508A CN101209410A CN 101209410 A CN101209410 A CN 101209410A CN A2006101715083 A CNA2006101715083 A CN A2006101715083A CN 200610171508 A CN200610171508 A CN 200610171508A CN 101209410 A CN101209410 A CN 101209410A
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Abstract
The invention provides a solidoid micro extraction head which comprises an extraction head body and extraction head fibers (6) which are arranged at the lower end of the extraction head body. The invention is characterized in that the extraction head fiber (6) consists of a metal wire and a carbon nanotube with the thickness of 30-100 Mum which is coated on the surface of the metal wire. The invention also provides a preparation method of the solidoid micro extraction head which comprises the following steps: part of the metal wire is cleaned and immersed into the ethanol solution of phenolic resin for 3 to 5 seconds, and a layer of the carbon nanotube is collected from carbon nanotube powder and then dried; the steps are repeated until the thickness of the coating layer of the carbon nanotube reaches 30-100 Mum; the metal wire coated with the carbon nanotube layer is placed into an oven for solidification; aging of the metal wire coated with the carbon nanotube layer takes place under the protection of nitrogen, and the extraction head fibers (6) are obtained; the prepared extraction head fibers are arranged at the lower end of the extraction head body, thus obtaining the solidoid micro extraction head.
Description
Technical field
The present invention relates to a kind of extracting head, particularly a kind of solid phase micro-extracting head and preparation method thereof.
Background technology
General extracting head structure 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 Zhi Zaiti 4, outer stainless steel tube 5 is formed, and described extracting head fiber 6 surfaces are manufactured with the extraction coating.
Supelco company is the main development and the manufacturer of present commercialization SPME (SPME) extracting head.The SPME extracting head that the said firm produces at present all is fixing phase coating to be coated with steep on quartz fibre as extracting fiber, these fixedly the phase coating composition mainly comprise dimethyl silicone polymer (PDMS), polyethylene glycol/dimethyl silicone polymer (CAR/PDMS), polyacrylate (PA), carbon molecular sieve/vinyl benzene (CW/DVB) or carbon molecular sieve/molecular template resin (CW/TPR), the preparation of these coatings all is the surface that high polymer is fixed on quartz fibre by the method for photocuring or high temperature heating, its machinery and heat endurance are all poor, under the situation of directly extraction, coating very easily ruptures and peels off, and quartz fibre itself fractures easily, and this has just limited the scope of application and the life-span of extracting head.
In order to overcome the shortcoming of extracting head frangibility, some researchers adopt stainless steel wire to replace fragile quartz fibre in recent years, to increase the mechanical performance of extracting head.Pawliszyn etc. on stainless steel wire by electric plating method polymerization one strata pyrrole as solid-phase micro-extraction coating (Anal.Chem.2001,73,55-63); This breadboard Huang etc. also is incorporated into the aniline voltolisation on the stainless steel wire as the extraction coating and extracts amino benzenes compounds in the water sample, have good selectivity (J.Chromatography A.2004,1048,257-262).
CNT is a novel absorption material, emerges in an endless stream in each Application for Field.CNT also is used to the research of extraction aspect in recent years.Wang etc. are used to extract PBDE fire retardant (Joumal of Chromatography A with the multi-walled carbon nano-tubes preparation on the quartz fibre surface, 2006,1137,8-14), key step is: at first multi-walled carbon nano-tubes is dispersed in the suspension that is mixed with 20mg/mL in the solvent dimethylformamide, then with this hanging drop to the quartz fibre surface, and be heated to 160 ℃ of solvent evaporated; Above-mentioned steps is 40 μ m up to coating layer thickness for several times repeatedly at last.Yet the extracting head fiber of the carbon nanotube coating of this method preparation still can't be avoided the defective that fractures easily, and is easier to come off by the coating ratio that physisorption makes, and has limited service life.
Summary of the invention
The objective of the invention is in order to overcome the defective of above-mentioned various extracting head, thereby a kind of firmer, low-cost, solid phase micro-extracting head of being easy to prepare is provided.
Another object of the present invention provides a kind of preparation method of above-mentioned solid phase micro-extracting head.
A kind of solid phase micro-extracting head provided by the invention, comprise extracting head body and the extracting head fiber 6 that is installed in extracting head body lower end, it is characterized in that described extracting head fiber 6 is by a wire and to be coated in thickness on the described wire surface be that the carbon nanotube layer of 30-100 μ m is formed.
Described carbon nanotube layer is SWCN layer, multi-walled carbon nano-tubes layer, perhaps is single wall or multi-walled carbon nano-tubes layer through perhydroxyl radical or carboxyl modified.
Described wire is stainless steel wire, platinum filament or spun gold.
The preparation method of solid phase micro-extracting head of the present invention is characterized in that, may further comprise the steps:
The part wiry that (1) will clean up immerses 3-5 second in the ethanolic solution of phenolic resins, takes out then, and then stickingly in carbon nanotube powder gets one deck CNT, and at room temperature dry; In the ethanolic solution of described phenolic resins, the mass percent concentration of phenolic resins is 40-60%;
(2) repeating step (1) is till the carbon nanotube coating thickness of described wire surface reaches 30-100 μ m;
(3) wire that is coated with carbon nanotube layer that step (2) is made places baking oven to solidify;
(4) wire that is coated with carbon nanotube layer after will solidifying is under nitrogen protection aging 0.5-2 hour, and aging temperature is 250-350 ℃, obtains the extracting head fiber;
(5) the extracting head fiber for preparing is installed in the lower end of extracting head body, obtains solid phase micro-extracting head.
Described CNT comprises SWCN, multi-walled carbon nano-tubes, perhaps is single wall or multi-walled carbon nano-tubes through perhydroxyl radical or carboxyl modified.
Described wire is stainless steel wire, platinum filament or spun gold.
Compare with existing solid phase micro-extracting head and method for production thereof, the present invention mainly contains following advantage:
1. easy fracture not, the present invention uses wire to replace quartz fibre in traditional solid phase micro-extracting head, has therefore increased the mechanical performance of extracting head;
2. be easy to preparation, adopt method of the present invention, CNT is adhered on the wire, all can realize the preparation of this extracting head in common laboratory with resistant to elevated temperatures phenolic resins;
3. flexibility can select have the CNT of different substituents according to the character of research purpose and object, as can selecting not CNT to nonpolar material through modifying, and the CNT that then can select for use hydroxyl modified to cross to polar substances;
4. low-cost, the stainless steel wire, CNT and the phenolic resins that are adopted in the method for the present invention are cheap and easy to get, and on average the cost of each extracting head is compared for eight or nine hundred yuan every with commercial PDMS extracting head less than 50 yuan, greatly reduces experimental cost;
5. the effect of extracting of extracting head of the present invention is improved than commercial PDMS extracting head.
Description of drawings
Fig. 1 is a kind of solid phase micro-extracting head structure chart.
Wherein, 1 is the plastics screw terminal, and 2 is interior stainless steel tube, and 3 is rubber gasket, and 4 is metal Zhi Zaiti, and 5 is outer stainless steel tube, and 6 is the extracting head fiber.
The specific embodiment
Below in conjunction with embodiment, novel solid phase micro extraction head of the present invention is described in further detail, but the invention is not restricted to these embodiment.
Fig. 1 has provided a kind of structure chart of solid phase micro-extracting head, plastics screw terminal 1, interior stainless steel tube 2, rubber gasket 3, metal Zhi Zaiti 4 and outer stainless steel tube 5 have constituted the body of extracting head jointly among the figure, the upper end of stainless steel tube 2 in plastics screw terminal 1 is installed in, outer stainless steel tube 5 is enclosed within on the interior stainless steel tube 2, the two ends of stainless steel tube in exposing, and outer stainless steel tube upper end is provided with metal Zhi Zaiti 4, described metal Zhi Zaiti 4 is provided with rubber gasket 3, wherein, outer stainless steel tube 5 diameter 0.55mm, the about 57mm of length; The about 0.30mm of interior stainless steel tube 2 diameters, the about 80mm of length, extracting head fiber 6 are installed in interior stainless steel tube 2 tops; Extracting head fiber 6 in the present embodiment is selected the stainless steel wire (also can select spun gold or platinum filament for use) of the about 0.1mm of diameter for use, and its surface-coated has the CNT (also can use carboxyl modified) of one deck through hydroxyl modified, and described CNT layer thickness is 30 μ m.
Extracting head preparation method's concrete steps of present embodiment are as follows:
(1) be the section that the stainless steel wire of 0.1mm is cut into 2 centimeter length with diameter, be immersed in the acetone ultrasonic cleaning 30 minutes, taking-up is dried; Part with stainless steel wire immerses 3-5 second in the phenolic resins ethanolic solution then, takes out, and is and then getting one deck CNT through sticking in the carbon nanotube powder of hydroxyl modified, and at room temperature dry 4-6 hour; In the ethanolic solution of described phenolic resins, the mass percent concentration of phenolic resins is 50%.
(2) repeating step (1) is till carbon nanotube coating thickness reaches 30 μ m;
(3) place baking oven to solidify the above-mentioned carbon nanotube coating that makes, according to the operation instruction that phenolic resins supplier provides, this step can be divided into three phases carries out, 80 ℃ of phase I solidification temperatures, 30 minutes hardening times; 120 ℃ of second stage solidification temperatures, 120 minutes hardening times; 180 ℃ of phase III solidification temperatures, 180 minutes hardening times; Through overcuring, what carbon nanotube layer was firm is bonded on the stainless steel wire;
(4) stainless steel wire that scribbles carbon nanotube layer after will solidifying is fixed on the lower end of solid phase micro-extracting head body, be made into the carbon nano-tube solid phase micro-extraction head, this extracting head is contained in the gas-chromatography injection port, and under nitrogen protection, be heated to 250 ℃ and wear out, ageing time is half an hour;
The above-mentioned CNT extracting head that makes is applied to extract amino benzenes compounds in the water sample, it has been carried out test repeatedly, have good stability, its relative standard deviation is 4.3-7.2% (three replication).In addition, utilize the solid phase micro-extracting head of present embodiment also to measure 3-methylaniline in the environmental water sample, 2-chloroaniline, 2,4-dimethylaniline, 3,4-dimethylaniline, 3, environmental contaminants such as 4-dichloroaniline find that its extraction efficiency doubles than commercial PDMS extracting head.
In the present embodiment, the wire that uses is stainless steel wire, what CNT was selected for use is not pass through the SWCN of modifying, in the phenolic resins ethanolic solution, the mass percent concentration of phenolic resins is 40%, the thickness of SWCN coating is 100 μ m, and aging condition is 350 ℃ and down continues 2 hours, and other structures and manufacturing conditions, step are identical with embodiment 1.
The extracting head that present embodiment is manufactured, extracted object is that organo-chlorine pesticide (comprises four kinds of isomers of BHC and P, P '-DDT, P, P '-dichloro-diphenyl-dichlorothane, P, P '-drip to drip she, O, P '-DDT), effect of extracting is compared with commercial PDMS extracting head, improve about 20% for BHC compounds efficient, and for the DDT compounds, about extraction efficiency doubles.
In the present embodiment, the wire that uses is stainless steel wire, what CNT was selected for use is not pass through the multi-walled carbon nano-tubes of modifying, in the phenolic resins ethanolic solution, the mass percent concentration of phenolic resins is 60%, the thickness of multi-wall carbon nano-tube pipe coating is 70 μ m, and aging condition is 300 ℃ and continues 1 hour, and other structures and manufacturing conditions, step are identical with embodiment 1.
The extracting head that present embodiment is manufactured, extracted object are benzene series thing (as benzene,toluene,xylene etc.), and effect of extracting is compared with commercial PDMS extracting head, and extraction efficiency has improved 50%.
Stainless steel wire among three top embodiment also can substitute with spun gold or platinum filament, CNT can be single wall or multi-walled carbon nano-tubes, also can be single wall or the multi-walled carbon nano-tubes through hydroxyl or carboxyl modified, the extracting head of Zhi Zuoing has same effect of extracting thus.
Claims (6)
1. solid phase micro-extracting head, comprise extracting head body and the extracting head fiber (6) that is installed in extracting head body lower end, it is characterized in that described extracting head fiber (6) is by a wire and to be coated in thickness on the described wire surface be that the carbon nanotube layer of 30-100 μ m is formed.
2. according to the described solid phase micro-extracting head of claim 1, it is characterized in that described carbon nanotube layer is SWCN layer, multi-walled carbon nano-tubes layer, perhaps is single wall or multi-walled carbon nano-tubes layer through perhydroxyl radical or carboxyl modified.
3. according to the described solid phase micro-extracting head of claim 1, it is characterized in that described wire is stainless steel wire, platinum filament or spun gold.
4. a method for preparing the described solid phase micro-extracting head of claim 1 is characterized in that, may further comprise the steps:
The part wiry that (1) will clean up immerses 3-5 second in the ethanolic solution of phenolic resins, takes out then, and then stickingly in carbon nanotube powder gets one deck CNT, and at room temperature dry; In the ethanolic solution of described phenolic resins, the mass percent concentration of phenolic resins is 40-60%;
(2) repeating step (1) is till the carbon nanotube coating thickness of described wire surface reaches 30-100 μ m;
(3) wire that is coated with carbon nanotube layer that step (2) is made places baking oven to solidify;
(4) wire that is coated with carbon nanotube layer after will solidifying is under nitrogen protection aging 0.5-2 hour, and aging temperature is 250-350 ℃, obtains the extracting head fiber;
(5) the extracting head fiber for preparing is installed in the lower end of extracting head body, obtains solid phase micro-extracting head.
5. according to the described method for preparing solid phase micro-extracting head of claim 4, it is characterized in that described CNT is SWCN, multi-walled carbon nano-tubes, perhaps is single wall or multi-walled carbon nano-tubes through perhydroxyl radical or carboxyl modified.
6. according to the described method for preparing solid phase micro-extracting head of claim 4, it is characterized in that described wire is stainless steel wire, platinum filament or spun gold.
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| CNA2006101715083A CN101209410A (en) | 2006-12-30 | 2006-12-30 | Solid phase micro-extracting head and preparation thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101357320B (en) * | 2008-09-18 | 2010-06-09 | 福州大学 | One-dimensional nano-array zinc oxide solid-phase micro-extraction coating and preparation method thereof |
| CN102489105A (en) * | 2011-11-29 | 2012-06-13 | 南昌航空大学 | Air treatment device |
| CN102019168B (en) * | 2009-09-09 | 2012-06-27 | 中国科学院兰州化学物理研究所 | Method for manufacturing carbon nanotube solid phase micro-extraction head |
| CN102728323A (en) * | 2012-07-11 | 2012-10-17 | 济南大学 | Preparation method of sliver-carbon nano-material composite coating metal wire solid-phase micro-extraction fiber |
| CN103055830A (en) * | 2012-12-26 | 2013-04-24 | 华南师范大学 | Preparation method for solid-phase micro-extraction head based on single-stranded DNA aptamer modified graphene oxide coating |
| CN105572268A (en) * | 2015-12-16 | 2016-05-11 | 中国烟草总公司郑州烟草研究院 | Solid phase microextraction and determination method for trace benzenes in water sample |
| CN106662571A (en) * | 2014-05-20 | 2017-05-10 | 斯佩威尔股份有限公司 | Sample extraction apparatus with micro elution bed design |
| CN108499549A (en) * | 2018-03-30 | 2018-09-07 | 广州质量监督检测研究院 | Solid phase micro-extracting head and preparation method thereof for being enriched with perfluorochemical |
| CN110327897A (en) * | 2019-06-28 | 2019-10-15 | 桂林理工大学 | A kind of titanate radical nanopipe SPME coating and the preparation method and application thereof |
| CN110681184A (en) * | 2019-09-29 | 2020-01-14 | 华中师范大学 | Multi-walled carbon nanotube/polyaniline composite coating based in-pipe solid phase micro-extraction column and online micro-extraction method |
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2006
- 2006-12-30 CN CNA2006101715083A patent/CN101209410A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101357320B (en) * | 2008-09-18 | 2010-06-09 | 福州大学 | One-dimensional nano-array zinc oxide solid-phase micro-extraction coating and preparation method thereof |
| CN102019168B (en) * | 2009-09-09 | 2012-06-27 | 中国科学院兰州化学物理研究所 | Method for manufacturing carbon nanotube solid phase micro-extraction head |
| CN102489105A (en) * | 2011-11-29 | 2012-06-13 | 南昌航空大学 | Air treatment device |
| CN102728323A (en) * | 2012-07-11 | 2012-10-17 | 济南大学 | Preparation method of sliver-carbon nano-material composite coating metal wire solid-phase micro-extraction fiber |
| CN102728323B (en) * | 2012-07-11 | 2014-03-26 | 济南大学 | Preparation method of sliver-carbon nano-material composite coating metal wire solid-phase micro-extraction fiber |
| CN103055830A (en) * | 2012-12-26 | 2013-04-24 | 华南师范大学 | Preparation method for solid-phase micro-extraction head based on single-stranded DNA aptamer modified graphene oxide coating |
| CN106662571A (en) * | 2014-05-20 | 2017-05-10 | 斯佩威尔股份有限公司 | Sample extraction apparatus with micro elution bed design |
| CN105572268A (en) * | 2015-12-16 | 2016-05-11 | 中国烟草总公司郑州烟草研究院 | Solid phase microextraction and determination method for trace benzenes in water sample |
| CN105572268B (en) * | 2015-12-16 | 2017-09-12 | 中国烟草总公司郑州烟草研究院 | The SPME assay method of Determination of Trace Benzene in a kind of water sample |
| CN108499549A (en) * | 2018-03-30 | 2018-09-07 | 广州质量监督检测研究院 | Solid phase micro-extracting head and preparation method thereof for being enriched with perfluorochemical |
| CN108499549B (en) * | 2018-03-30 | 2021-12-14 | 广州质量监督检测研究院 | Solid phase micro-extraction head for enriching perfluoro compounds and preparation method thereof |
| CN110327897A (en) * | 2019-06-28 | 2019-10-15 | 桂林理工大学 | A kind of titanate radical nanopipe SPME coating and the preparation method and application thereof |
| CN110681184A (en) * | 2019-09-29 | 2020-01-14 | 华中师范大学 | Multi-walled carbon nanotube/polyaniline composite coating based in-pipe solid phase micro-extraction column and online micro-extraction method |
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Open date: 20080702 |