CN1331551C - Cup[4] open chain crown ether solid-phase micro extraction head and making method therefor - Google Patents
Cup[4] open chain crown ether solid-phase micro extraction head and making method therefor Download PDFInfo
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- CN1331551C CN1331551C CNB2005100191847A CN200510019184A CN1331551C CN 1331551 C CN1331551 C CN 1331551C CN B2005100191847 A CNB2005100191847 A CN B2005100191847A CN 200510019184 A CN200510019184 A CN 200510019184A CN 1331551 C CN1331551 C CN 1331551C
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Abstract
The present invention discloses an extraction head for a cup [4] open-chain crown ester solid-phase microextraction and a preparation method thereof. The extraction head is characterized in that a cup [4] open-chain crown ester / hydroxy silicone oil composite coating layer is bonded on a surface of quartz fiber. The extraction head is prepared by a method that collosol-gel and free radicals are initiated to be crossly linked and combined. The extraction head for solid-phase microextraction provided by the present invention has the advantages of high thermal stability, solvent flushing resistance capability and strong alkali resistance capability, long service life, good adsorption capacity on polarity and nonpolarity fragrant and fatty compounds, and significant application prospect on fields of food analysis, environmental monitoring and excitant detection. The method for preparing the extraction head is simple and quick, and has good reproducibility.
Description
Technical field
The present invention relates to a kind of SPME (SPME) extracting head and preparation method thereof, especially the quartz fibre surface bond of extracting head has the solid phase micro-extraction extraction head and preparation method thereof of the composite coating of cup [4] open chain crown ether and hydroxy silicon oil, belong to chemical field, also belong to the analytical chemistry field.
Technical background
SPME is a kind of simple, quick, sensitive, the solvent-free sample-pretreating method that grows up on the SPE basis.Wherein, solid phase micro-extraction extraction head is the core of this technology.Although solid phase micro-extraction technique had obtained development fast in recent years, also there are some urgent problems.At first, most commercial extracting head are that employing physics is coated with stain and partial cross-linked method prepares, and operating temperature is low, and a little less than the anti-solvent washing ability, service life is short.Secondly, existing solid phase micro-extraction extraction head coating kind is few, and sensitivity is lower, thereby has limited its range of application widely.
Summary of the invention
For solving problems of the prior art, the invention provides a kind of new solid phase micro-extraction extraction head and preparation method thereof, this solid phase micro-extraction extraction head is a coating material with cup [4] open chain crown ether and the hydroxy silicon oil that contains the vinyl active group, adopts sol-gel and free radical to cause the crosslinked method preparation that combines.
The technical solution adopted in the present invention is as follows:
A kind of cup [4] open chain crown ether solid phase micro-extraction extraction head, its special character are the surface bond of its quartz fibre composite coating that cup [4] open chain crown ether and hydroxy silicon oil are arranged (C[4] open-chain crownether/OH-TSO).
Wherein cup [4] open chain crown ether coating material is for containing vinyl active group 5,11,17,23-four-tert-butyl group-25,27-two (2-allyl oxygen ethyoxyl)-26,28-dihydroxy cup [4] aromatic hydrocarbons.
The present invention also provides the preparation method of above-mentioned cup [4] open chain crown ether/hydroxy silicon oil solid phase micro-extraction extraction head, and step is as follows:
(1) gets cup [4] open chain crown ether that 10-60mg contains the vinyl active group, dilute with 140-250 μ L carrene, adding quality is cup [4] open chain crown ether quality 1.5-10 hydroxy silicon oil doubly, add 80-120 μ L tetraethoxysilane or MTMS again, add 30-60 μ L VTES or gamma-methyl allyl acyloxypropyl trimethoxysilane, adding the 6-10mg benzophenone fully mixes, adding 30-100 μ L contains the trifluoroacetic acid of 3-10% (volume ratio) water, the containing hydrogen silicone oil that adds 0-15 μ L then, with gains sonic oscillation 3-10 minute, under 8000-16000r/min centrifugal 4-8 minute then, it was standby to take out supernatant liquor.
(2) quartz fibre one end that will remove the drying of protective layer inserted in the colloidal sol clear liquid about 10-60 minute, and repeatable operation obtains certain thickness coating for several times, took out back placement 8-24 hour in drier, and under uviol lamp photocuring 10-60 minute then, at N
2Protection promptly gets required solid phase micro-extraction extraction head in 250-320 ℃ of aging 2-3h down.
As shown from the above technical solution, bonding provided by the invention has the solid phase micro-extraction extraction head of the composite coating of cup [4] open chain crown ether and hydroxy silicon oil to adopt the sol-gel process preparation, and calixarenes is the third generation host molecule after cyclodextrin and crown ether, and organic molecule is had good recognition capability.Open chain crown ether is a kind of crown ether of being similar to-CH that has
2CH
2The acyclic polyetherization compound of O-construction unit, it remains with the selective coordination ability of crown ether to polar compound.Cup [4] open chain crown ether combines the advantage of cup [4] aromatic hydrocarbons and two kinds of host compounds of open chain crown ether, utilizing its dual identification, cooperative effect to improve its extraction and accumulation ability to polarity and non-polar compound, is the extremely promising solid-phase micro-extraction coating material of a class.Therefore this extracting head has high heat endurance and solvent stability, and long service life all has good extracting power to polarity and nonpolar fragrance and aliphatic compound, and preparation process is simple, fast, favorable reproducibility.
Description of drawings
Fig. 1 is the comparison to aliphatic acid, pure and mild ester type compound extracting power in the beer of prepared cup [4] open chain crown ether/hydroxy silicon oil extracting head of the present invention and commercial PDM S, PDMS/DVB and PA extracting head.
Fig. 2 is the comparison to urine sample epheday intermedia alkali and pseudoephedrine compounds extracting power of cup [4] open chain crown ether/hydroxy silicon oil extracting head and commercial PDM S and PA extracting head.
The specific embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is further described, wherein used cup [4] open chain crown ether is to contain 5 of vinyl active group, 11,17,23-four-tert-butyl group-25,27-two (2-allyl oxygen ethyoxyl)-26,28-dihydroxy cup [4] aromatic hydrocarbons (C[4] open-chain crown ether).This cup [4] open chain crown ether can be synthetic with conventional method in the laboratory.Hydroxy silicon oil (OH-TSO, molecular weight are 3000-5000) is used and the research center available from Chengdu silicon, tetraethoxysilane, and VTES, containing hydrogen silicone oil (molecular weight is 1000-2000) is available from the Wuhan University chemical plant.Trifluoroacetic acid is available from the Beijing Chemical Plant.
Embodiment 1:
Get 30mg cup [4] open chain crown ether, dilute with 160 μ L carrene, add 80mg hydroxy silicon oil, 100 μ L tetraethoxysilanes, 50 μ L gamma-methyl allyl acyloxypropyl trimethoxysilanes, adding the 12mg benzophenone fully mixes, add 60 μ L and contain the trifluoroacetic acid of 5% (volume ratio) water, add 10 μ L containing hydrogen silicone oils then, continued sonic oscillation 5 minutes, 12000r/min centrifugation 5 minutes, the taking-up upper strata stillness of night was standby.Quartz fibre one end that removes the drying of protective layer is inserted in the colloidal sol clear liquid about 50 minutes the thickness repeatable operation of required extracting head (look for several times), take out the back and placed 18 hours in drier, photocuring 50 minutes under uviol lamp then is at N
2Protection down in 280 ℃ at the aging 2h of gas-chromatography vaporizer, the extracting head thickness of gained is 45-75 μ m.
Embodiment 2:
Get 50mg cup [4] open chain crown ether, dilute with 200 μ L carrene, add 100mg hydroxy silicon oil, 110 μ L tetraethoxysilanes, 50 μ L VTESs, adding the 9mg benzophenone fully mixes, add 100 μ L and contain the trifluoroacetic acid of 5% (volume ratio) water, add 12 μ L containing hydrogen silicone oils then, continued sonic oscillation 8 minutes, 12000r/min centrifugation 8 minutes, the taking-up upper strata stillness of night was standby.Quartz fibre one end that removes the drying of protective layer is inserted in the colloidal sol clear liquid about 40 minutes the thickness repeatable operation of required extracting head (look for several times), take out the back and placed 16 hours in drier, photocuring 40 minutes under uviol lamp then is at N
2Protection down in 300 ℃ at the aging 2h of gas-chromatography vaporizer, the extracting head thickness of gained is 45-85 μ m.
Embodiment 3:
Get 10mg cup [4] open chain crown ether, dilute with 140 μ L carrene, add the 100mg hydroxy silicon oil, add 80 μ L MTMSs, add 30 μ L VTESs, adding the 6mg benzophenone fully mixes, add 30 μ L and contain the trifluoroacetic acid of 5% (volume ratio) water, add the containing hydrogen silicone oil of 8 μ L then, continued sonic oscillation 3 minutes, under 8000r/min centrifugal 4 minutes, it was standby to take out supernatant liquor.Quartz fibre one end that removes the drying of protective layer was inserted in the colloidal sol clear liquid about 20 minutes, and repeatable operation obtains certain thickness coating for several times, takes out the back and places 8 hours in drier, and photocuring 30 minutes under uviol lamp then is at N
2Protection in 250 aging 2.5h, promptly gets required solid phase micro-extraction extraction head down.
Embodiment 4:
Get 60mg cup [4] open chain crown ether, dilute with 250 μ L carrene, add the 90mg hydroxy silicon oil, add 120 μ L tetraethoxysilanes, add 60 μ L VTESs, adding the 10mg benzophenone fully mixes, add 70 μ L and contain the trifluoroacetic acid of 10% (volume ratio) water, add the containing hydrogen silicone oil of 15 μ L then, continued sonic oscillation 10 minutes, under 16000r/min centrifugal 8 minutes, it was standby to take out supernatant liquor.Quartz fibre one end that removes the drying of protective layer was inserted in the colloidal sol clear liquid about 60 minutes, and repeatable operation obtains certain thickness coating for several times, takes out the back and places 24 hours in drier, and photocuring 60 minutes under uviol lamp then is at N
2Protection promptly gets required solid phase micro-extraction extraction head down in 320 ℃ of aging 3h.
Embodiment 5:
Get 20mg cup [4] open chain crown ether, dilute with 180 μ L carrene, add the 120mg hydroxy silicon oil, add 100 μ L tetraethoxysilanes, add 40 μ L VTESs, add the 8mg benzophenone and fully mix, add 50 μ L and contain the trifluoroacetic acid of 3% (volume ratio) water, continued sonic oscillation 6 minutes, under 12000r/min centrifugal 6 minutes, it was standby to take out supernatant liquor.Quartz fibre one end that removes the drying of protective layer was inserted in the colloidal sol clear liquid about 30 minutes, and repeatable operation obtains certain thickness coating for several times, takes out the back and places 12 hours in drier, and photocuring 20 minutes under uviol lamp then is at N
2Protection promptly gets required solid phase micro-extraction extraction head in 300 ℃ of aging 2.5h down.
The present invention adopts sol-gel and the crosslinked method that combines of free radical initiation to prepare above-mentioned cup [4] open chain crown ether/hydroxy silicon oil solid phase micro-extraction extraction head.This technical scheme has related to the hydrolysis of two kinds of Organometallic precursors, a kind of is tetraethoxysilane (or MTMS), its hydrolysate forms the three-dimensional silica gel skeleton of an inorganic medium by polycondensation reaction, another kind is cross-linking reagent VTES (or gamma-methyl allyl acyloxypropyl trimethoxysilane), its hydrolysate comprises two kinds of active function groups, silicon hydroxyl and vinyl, therefore both can form an organic whole, and can cause cross-linking reaction again by the free radical of vinyl and will contain cup [4] open chain crown ether bond of vinyl active group in composite coating by the polycondensation reaction and the silica gel skeleton of silicon hydroxyl.Utilize CH
2Cl
2Do infrared spectrogram with the extracting head of washing, the characteristic peak that still contains cup [4] open chain crown ether: 1484.00cm-1 (v Ar-C=C-), 1361.30cm-1 (v Ar-C=C-) and 3357.20cm-1 (v Ar-OH) illustrate that cup [4] open chain crown ether is bonded in the coating.
Adopt cup [4] open chain crown ether/hydroxy silicon oil extracting head of technical scheme preparation of the present invention, owing between coating and fiber surface and the coating material strong chemical bonding effect has taken place, therefore have very high heat endurance, chemical stability and anti-solvent washing, anti-highly basic ability, improve the service life of extracting head, expanded the range of application of SPME widely.Adopt technical scheme of the present invention, preparation process is simple, quick, the probe favorable reproducibility.
Calixarenes is the cyclic oligomer that a class is generated through polycondensation reaction by phenol and formaldehyde.The calixarenes molecule has the cavity of the size of can regulating, and its upper limb and lower edge are easy to carry out chemical modification, be easy to and non-polar compound generation hydrophobic interaction, π-π interaction, dipole-dipole interaction and inclusion effect, non-polar compound is had good extracting power.Open chain crown ether is a kind of crown ether of being similar to-CH that has
2CH
2The acyclic polyetherization compound of O-construction unit, it remains with the selective coordination ability of crown ether.Because the class ring cavity structure of open chain crown ether and high cloud density are easy to and polar compound generation dipole-dipole interaction and interaction of hydrogen bond, and polar compound is had good adsorption capacity.Cup [4] open chain crown ether combines the advantage of cup [4] aromatic hydrocarbons and two kinds of host compounds of open chain crown ether, utilizes its dual identification, cooperative effect to improve its extraction and accumulation ability (as phenolic compound, alcohol compound, fatty acid, ester type compound and ephedrine and pseudoephedrine class excitant) to polarity and nonpolar fragrance and aliphatic compound.
Table 1 is the equilibrium distribution coefficient Log K of phenols sample in the prepared cup of the present invention [4] open chain crown ether/hydroxy silicon oil and commercial PDM S, PDMS/DVB and the PA extracting head extraction water
SpmeComparison.As can be seen from the table, cup [4] open chain crown ether/hydroxy silicon oil extracting head has stronger polarity, to the Log K of all phenols samples
SpmeValue all is far longer than PDMS and PDMS/DVB extracting head, to most of phenols samples, and its Log K
SpmeValue is also greater than the PA extracting head of polarity.
Table 1 compares the equilibrium distribution coefficient Log K of phenols sample in cup [4] open chain crown ether/hydroxy silicon oil and commercial PDM S, PDMS/DVB and the PA extracting head extraction water
Spme
| Compound | Log K spme | |||
| C[4]open-chain crown ether/OH-TSO(75μm) | PDMS (100μm) | PDMS/DVB (65μm) | PA(85 μm) | |
| 2-chlorophenol 2-nitrophenols 2-cresols phenol 4-cresols 2,4-xylenol 2,4 two chlorophenols | 3.40 3.63 3.14 2.62 3.60 2.83 4.43 | 0.91 1.01 0.60 -0.10 1.20 0.40 1.51 | 1.49 1.64 1.35 0.69 1.99 1.26 2.29 | 3.40 2.84 3.13 2.52 3.61 2.74 4.21 |
Fig. 1 is the comparison to aliphatic acid, pure and mild ester type compound extracting power in the beer of prepared cup [4] open chain crown ether/hydroxy silicon oil extracting head of the present invention and commercial PDM S, PDMS/DVB and PA extracting head.From figure as can be known, cup [4] open chain crown ether/hydroxy silicon oil extracting head all has good effect of extracting to alcohols, acids and the nonpolar ester type compound of polarity.
Fig. 2 is the comparison to urine sample epheday intermedia alkali and pseudoephedrine compounds extracting power of cup [4] open chain crown ether/hydroxy silicon oil extracting head and commercial PDM S and PA extracting head.From figure as can be known, cup [4] open chain crown ether/hydroxy silicon oil extracting head has very strong adsorption capacity to the ephedrine and the pseudoephedrine class excitant of polarity.
Measure ephedrine and the pseudoephedrine compounds in alcohol, aliphatic acid and ester class flavor substance and the urine sample in phenolic compound, the beer in the water with the prepared extracting head of the present invention, detectability is low, the range of linearity is wide, favorable reproducibility, thereby all has good application prospects in environmental monitoring, local flavor analysis and drug-testing field.
Claims (3)
1. a cup [4] open chain crown ether solid phase micro-extraction extraction head comprises quartz fibre, it is characterized in that: the composite coating that cup [4] open chain crown ether/hydroxy silicon oil is arranged at the quartz fibre surface bond.
2. cup [4] open chain crown ether solid phase micro-extraction extraction head according to claim 1 is characterized in that: cup [4] open chain crown ether coating material is for containing vinyl active group 5,11,17,23-four-tert-butyl group-25,27-two (2-allyl oxygen ethyoxyl)-26,28-dihydroxy cup [4] aromatic hydrocarbons.
3. method for preparing the described cup of claim 1 [4] open chain crown ether solid phase micro-extraction extraction head is characterized in that adopting following steps:
(1) gets cup [4] open chain crown ether that 10-60mg contains the vinyl active group, dilute with 140-250 μ L carrene, adding quality is cup [4] open chain crown ether quality 1.5-10 hydroxy silicon oil doubly, add 80-120 μ L tetraethoxysilane or MTMS again, add 30-60 μ L VTES or gamma-methyl allyl acyloxypropyl trimethoxysilane, adding the 6-10mg benzophenone fully mixes, adding 30-100 μ L contains the trifluoroacetic acid of 3-10% (volume ratio) water, the containing hydrogen silicone oil that adds 0-15 μ L then, with gains sonic oscillation 3-10 minute, under 8000-16000r/min centrifugal 4-8 minute then, it was standby to take out supernatant liquor.
(2) quartz fibre one end that will remove the drying of protective layer inserted in the colloidal sol clear liquid about 10-60 minute, and repeatable operation obtains certain thickness coating for several times, took out back placement 8-24 hour in drier, and under uviol lamp photocuring 10-60 minute then, at N
2Protection promptly gets required solid phase micro-extraction extraction head in 250-320 ℃ of aging 2-3 h down.
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| CNB2005100191847A CN1331551C (en) | 2005-07-29 | 2005-07-29 | Cup[4] open chain crown ether solid-phase micro extraction head and making method therefor |
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| CNB2005100191847A CN1331551C (en) | 2005-07-29 | 2005-07-29 | Cup[4] open chain crown ether solid-phase micro extraction head and making method therefor |
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| CN1331551C true CN1331551C (en) | 2007-08-15 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1039288A2 (en) * | 1999-03-26 | 2000-09-27 | Gerstel Systemtechnik GmbH & Co. KG | Method for solid phase micro-extraction, analysis and collector therefor |
| CN1316395A (en) * | 2001-03-26 | 2001-10-10 | 武汉大学 | Solid-phase microextracting coated layer containing fullerene polymer |
| CN2455328Y (en) * | 2000-11-30 | 2001-10-24 | 武汉大学 | Simple solid phase micro-extractor |
| US6405608B1 (en) * | 2000-01-25 | 2002-06-18 | Sandia Corporation | Method and apparatus for optimized sampling of volatilizable target substances |
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- 2005-07-29 CN CNB2005100191847A patent/CN1331551C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1039288A2 (en) * | 1999-03-26 | 2000-09-27 | Gerstel Systemtechnik GmbH & Co. KG | Method for solid phase micro-extraction, analysis and collector therefor |
| US6405608B1 (en) * | 2000-01-25 | 2002-06-18 | Sandia Corporation | Method and apparatus for optimized sampling of volatilizable target substances |
| CN2455328Y (en) * | 2000-11-30 | 2001-10-24 | 武汉大学 | Simple solid phase micro-extractor |
| CN1316395A (en) * | 2001-03-26 | 2001-10-10 | 武汉大学 | Solid-phase microextracting coated layer containing fullerene polymer |
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