CN1820814A - Solid phase micro extraction extracting head of aluminium oxide and hydroty silicon oil composite coating and its prepn - Google Patents
Solid phase micro extraction extracting head of aluminium oxide and hydroty silicon oil composite coating and its prepn Download PDFInfo
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- CN1820814A CN1820814A CN 200610018190 CN200610018190A CN1820814A CN 1820814 A CN1820814 A CN 1820814A CN 200610018190 CN200610018190 CN 200610018190 CN 200610018190 A CN200610018190 A CN 200610018190A CN 1820814 A CN1820814 A CN 1820814A
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Abstract
The present invention relates to solid phase micro extracting head possessing one composite coating of bonded alumina and hydroxyl silicon oil on the surface of quartz fiber. The present invention also provides the preparation process of the extracting head, and preparation process includes adding dichloromethane, isopropanol and acetylacetone into isobutynol aluminum and ultrasonic dissolving, adding hydroxyl silicon oil, ultrasonic vibration and centrifuging, and taking the supernatant; inserting one end of the quartz fiber through eliminating the protecting layer and drying into the supernatant, drying after taking out, and ageing under the protection of N2 to obtain the micro extracting head. The present invention has porous structure, high heat stability and chemical stability, wide stable pH range, high strong alkali resistance, long service life, high extracting efficiency on polar fatty acid, phenol, alcohol, aldehyde and amine, and wide application in food analysis and environment monitoring.
Description
Technical field
The present invention relates to a kind of solid phase micro-extraction extraction head and preparation method thereof, particularly a kind of aluminium oxide and hydroxy silicon oil composite coating solid phase micro-extraction extraction head and preparation method thereof belong to chemical field, also belong to the analytical chemistry field.
Technical background
Solid phase micro-extraction technique is a kind of novel sample pretreatment technology that grows up the nineties.This technology centralized procurement sample, extraction, concentrate and sample introduction in one, have the organic solvent of need not, amount of samples is few, realizes automation easily, and is with other analytical instrument coupling, easy and simple to handle easily, quick, expense is few and install advantages such as small and exquisite.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.Because the advantage of sol-gel process inherence, be that the composite organic-inorganic material of matrix has obtained in the SPME field using widely with the silica.Although the coating material that with the silica is matrix has lot of advantages, but still there are some defectives, wherein topmost is exactly that the pH scope of application is narrow, generally the pH stability range of silica gel is between the 2-8, what adopt the sol-gel process preparation is that the material of matrix can improve its pH stability to a certain extent with the silica, but coating still has damage under the highly basic condition.
Summary of the invention
The object of the present invention is to provide a kind of is the solid phase micro-extraction extraction head and preparation method thereof of matrix, i.e. aluminium oxide/hydroxy silicon oil composite coating solid phase micro-extraction extraction head and preparation method thereof with the aluminium oxide.This extracting head should have high heat endurance and chemical stability, the wide pH scope of application, and long service life, good preparation reappearance, and polar compound had characteristics such as good extracting power.
For achieving the above object, the technical solution adopted in the present invention is as follows:
A kind of aluminium oxide and hydroxy silicon oil composite coating solid phase micro-extraction extraction head comprise that quartz fibre reaches the coating attached to the quartz fibre surface, and described coating is aluminium oxide and the hydroxy silicon oil composite bed that is bonded in the quartz fibre surface.
The present invention also provides the preparation method of above-mentioned solid phase micro-extraction extraction head: get the 24.6-147.6mg isobutanol aluminum, add 80-120 μ l carrene and 300-500 μ l isopropyl alcohol, add 5-40 μ l acetylacetone,2,4-pentanedione, ultrasonic dissolution, add isobutanol aluminum 0.6-4 hydroxy silicon oil (mass ratio) doubly, add the containing hydrogen silicone oil of 0-15 μ l, sonic oscillation 8-20 minute, under 8000-16000r/min centrifugal 3-8 minute, 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 10-40 minute, vertically pull out, repeatable operation obtains certain thickness coating for several times, takes out the back and places 8-24h in drier, at N
2Protection promptly gets required solid phase micro-extraction extraction head down in 320-360 ℃ of aging 2-3h.
Adopt the aluminium oxide/hydroxy silicon oil extracting head of the present invention's preparation, owing between coating and fiber surface and the coating material strong chemical bonding effect has taken place, therefore have very high heat endurance and chemical stability, has wide pH stability range, improved the service life of extracting head, this extracting head has loose structure simultaneously, prepares favorable reproducibility, has therefore expanded the range of application of SPME widely.
Measure polarity flavor substance in phenolic compound in the water and beer and the sour milk with the prepared extracting head of the present invention, as pure and mild fatty acid compound, detectability is low, the range of linearity is wide, favorable reproducibility, therefore has good application prospects in environmental monitoring and flavour of food products analysis field.
Description of drawings
Fig. 1 is the sem photograph of extracting head surface texture;
After Fig. 2 soaks under condition of different pH for the soldier gets head the soldier get efficiency chart;
Fig. 3 gets head and commercial PDM S for the soldier, and PDMS/DVB and PA are to the comparison of aliphatic acid extraction efficiency.
The specific embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is further described:
In the embodiment of the invention, hydroxy silicon oil is used and the research center available from Chengdu silicon, and containing hydrogen silicone oil is available from the Wuhan University chemical plant, and acetylacetone,2,4-pentanedione is available from Shanghai Chemical Plant, and isobutanol aluminum is available from German MERCK company.
Embodiment 1:
Get the 98.4mg isobutanol aluminum, add 100 μ l carrene and 400 μ l isopropyl alcohols, add 20 μ l acetylacetone,2,4-pentanediones, ultrasonic dissolution adds the 90mg hydroxy silicon oil, adds the containing hydrogen silicone oil of 10 μ l, continue sonic oscillation 15min, centrifugal 5min under 12000r/min, it is standby to take out supernatant liquor.Quartz fibre one end that removes the drying of protective layer is inserted about 20min in the colloidal sol clear liquid, vertically pull out, repeatable operation obtains certain thickness coating for several times, takes out the back and place 12h in drier, then at N
2Protection is down in 340 ℃ of aging 2h, and promptly the extracting head thickness of gained is 60-85 μ m.
Embodiment 2:
Get the 147.6mg isobutanol aluminum, add 100 μ l carrene and 500 μ l isopropyl alcohols, add 40 μ l acetylacetone,2,4-pentanediones, ultrasonic dissolution adds the 90mg hydroxy silicon oil, adds the containing hydrogen silicone oil of 15 μ l, continue sonic oscillation 20min, centrifugal 8min under 16000r/min, it is standby to take out supernatant liquor.Quartz fibre one end that removes the drying of protective layer is inserted about 10min in the colloidal sol clear liquid, vertically pull out, repeatable operation obtains certain thickness coating for several times, takes out the back and place 24h in drier, then at N
2Protection is down in 320 ℃ of aging 3h, and promptly the extracting head thickness of gained is 45-75 μ m.
Embodiment 3:
Get the 24.6mg isobutanol aluminum, add 80 μ l carrene and 300 μ l isopropyl alcohols, add 5 μ l acetylacetone,2,4-pentanediones, ultrasonic dissolution adds the 73.8mg hydroxy silicon oil, continues sonic oscillation 8min, centrifugal 3min under 8000r/min, and it is standby to take out supernatant liquor.Quartz fibre one end that removes the drying of protective layer is inserted about 40min in the colloidal sol clear liquid, vertically pull out, repeatable operation obtains certain thickness coating for several times, takes out the back and place 8h in drier, then at N
2Protection is down in 360 ℃ of aging 2.5h, and promptly the extracting head thickness of gained is 40-65 μ m.
Embodiment 4:
Get the 49.2mg isobutanol aluminum, add 120 μ l carrene and 360 μ l isopropyl alcohols, add 10 μ l acetylacetone,2,4-pentanediones, ultrasonic dissolution adds the 60mg hydroxy silicon oil, adds the containing hydrogen silicone oil of 8 μ l, continue sonic oscillation 10min, centrifugal 5min under 12000r/min, it is standby to take out supernatant liquor.Quartz fibre one end that removes the drying of protective layer is inserted about 30min in the colloidal sol clear liquid, vertically pull out, repeatable operation obtains certain thickness coating for several times, takes out the back and place 16h in drier, then at N
2Protection is down in 350 ℃ of aging 2h, and the extracting head thickness of gained is 50-80 μ m.
Embodiment 5:
Get the 36.9mg isobutanol aluminum, add 100 μ l carrene and 400 μ l isopropyl alcohols, add 10 μ l acetylacetone,2,4-pentanediones, ultrasonic dissolution adds the 147.6mg hydroxy silicon oil, continues sonic oscillation 12min, centrifugal 5min under 8000r/min, and it is standby to take out supernatant liquor.Quartz fibre one end that removes the drying of protective layer is inserted about 15min in the colloidal sol clear liquid, vertically pull out, repeatable operation obtains certain thickness coating for several times, takes out the back and place 16h in drier, then at N
2Protection is down in 330 ℃ of aging 3h, and promptly the extracting head thickness of gained is 45-70 μ m.
Adopt the aluminium oxide/hydroxy silicon oil extracting head of technical scheme preparation of the present invention, because the alumina host surface has the lewis acidity site, can with the lewis base property compound, as aliphatic acid, phenol, alcohol, aldehyde and amineization and thing generation Lewis Acids and Bases interact, be the usually said ligand exchange effect that gets, therefore these polar compounds had very high extraction efficiency.
The present invention is presoma with the isobutanol aluminum, is slow dose with acetylacetone,2,4-pentanedione, adopts sol-gel process to prepare this novel aluminium oxide/hydroxy silicon oil solid phase micro-extraction extraction head.Sol-gel alumina is relatively found to have occurred the characteristic peak 905.95cm of Si-O-Al key in sol-gel alumina/hydroxy silicon oil coating behind the infrared spectrum of aluminium oxide/hydroxy silicon oil coating and pure hydroxy silicon oil
-1, thereby can prove firm chemical bonding effect has taken place between hydroxy silicon oil and the alumina host.
Fig. 1 shows that sol-gel alumina/hydroxy silicon oil coating has very significantly loose structure.
Fig. 2 has shown the pH stability of sol-gel alumina/hydroxy silicon oil coating.Two different probes were soaked 12 hours under different acidity (A) and alkalescence (B) pH condition respectively, the variation of comparative coatings extraction efficiency then, the result shows, aluminium oxide/hydroxy silicon oil coating is after soaking 12 hours under the strong acid condition of pH0 and under the highly basic condition of pH14, tangible change does not take place in extraction efficiency, therefore this extracting head has high chemical stability, has wide pH stability range.
Table 1 is the reappearance of sol-gel alumina/hydroxy silicon oil coating preparation.As can be known, no matter be the same batch or the extracting head of different prepared in batches from table, its reappearance is all fine.
The reappearance of table 1 sol-gel alumina/hydroxy silicon oil coating preparation
| Analytes | Reproducibility(％) | |
| Fiber-to-fiber(n＝3) | Batch-to-batch(n＝3) | |
| 1-Propanol Isobutanol 1-Butanol Isoamyl alcohol 2-Hexanol 1-Hexanol 2-Octanol 1-Heptanol Isooctanol 2-Nonanol 1-Octanol 1-Decanol β-Phenylethanol Propionic acid Isobutyric acid Valeric acid Hexanoic acid | 4.9 5.3 4.9 5.4 4.8 4.2 5.2 3.8 3.2 5.2 1.3 4.5 4.8 1.7 2.2 3.5 3.2 | 5.8 4.4 5.5 4.9 5.0 3.3 6.0 5.5 3.7 5.8 3.6 5.8 5.5 5.3 5.7 4.8 4.9 |
| Heptanoic acid Octanoic acid | 1.3 3.9 | 3.5 5.3 |
Fig. 3 has compared extracting head and commercial PDM S, and PDMS/DVB and PA are to the aliphatic acid extraction efficiency.Owing to have strong ligand exchange effect between aluminium oxide/hydroxy silicon oil coating and the aliphatic acid, so extraction efficiency is all higher than three kinds of commercial extracting head.
Claims (2)
1. aluminium oxide and hydroxy silicon oil composite coating solid phase micro-extraction extraction head comprise quartz fibre and attached to the coating on quartz fibre surface, it is characterized in that: described coating is aluminium oxide and the hydroxy silicon oil composite bed that is bonded in the quartz fibre surface.
2. the preparation method of aluminium oxide as claimed in claim 1 and hydroxy silicon oil composite coating solid phase micro-extraction extraction head, it is characterized in that: get the 24.6-147.6mg isobutanol aluminum, add 80-120 μ l carrene and 300-500 μ l isopropyl alcohol, add 5-40 μ l acetylacetone,2,4-pentanedione, ultrasonic dissolution, add isobutanol aluminum 0.6-4 hydroxy silicon oil (mass ratio) doubly, the containing hydrogen silicone oil that adds 0-15 μ l, sonic oscillation 8-20 minute, under 8000-16000r/min centrifugal 3-8 minute, 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 10-40 minute, vertically pull out, repeatable operation obtains certain thickness coating for several times, takes out the back and places 8-24h in drier, at N
2Protection promptly gets required solid phase micro-extraction extraction head down in 320-360 ℃ of aging 2-3h.
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| CNB2006100181905A CN100369647C (en) | 2006-01-18 | 2006-01-18 | Solid phase micro extraction extracting head of aluminium oxide and hydroty silicon oil composite coating and its prepn |
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| CNB2006100181905A CN100369647C (en) | 2006-01-18 | 2006-01-18 | Solid phase micro extraction extracting head of aluminium oxide and hydroty silicon oil composite coating and its prepn |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101920193A (en) * | 2010-08-20 | 2010-12-22 | 华中农业大学 | Sol-gel ionic liquid solid phase microextraction extraction fiber and preparation method thereof |
| CN102539609A (en) * | 2011-12-31 | 2012-07-04 | 青岛啤酒股份有限公司 | Detection method for measuring free fatty acid in beer through methyl esterification in bottle-headspace SPME (solid-phase micro-extraction)-gas chromatography and mass spectrum |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6759126B1 (en) * | 1998-09-21 | 2004-07-06 | University Of South Florida | Solid phase microextraction fiber structure and method of making |
| CN1141577C (en) * | 2001-03-26 | 2004-03-10 | 武汉大学 | Making method of crown ether solid phase extracting probe |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101920193A (en) * | 2010-08-20 | 2010-12-22 | 华中农业大学 | Sol-gel ionic liquid solid phase microextraction extraction fiber and preparation method thereof |
| CN101920193B (en) * | 2010-08-20 | 2012-06-27 | 华中农业大学 | Sol-gel ionic liquid solid phase microextraction extraction fiber and preparation method thereof |
| CN102539609A (en) * | 2011-12-31 | 2012-07-04 | 青岛啤酒股份有限公司 | Detection method for measuring free fatty acid in beer through methyl esterification in bottle-headspace SPME (solid-phase micro-extraction)-gas chromatography and mass spectrum |
| CN102539609B (en) * | 2011-12-31 | 2014-07-16 | 青岛啤酒股份有限公司 | Detection method for measuring free fatty acid in beer through methyl esterification in bottle-headspace SPME (solid-phase micro-extraction)-gas chromatography and mass spectrum |
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