CN102008945A - Manufacturing method of beta-cyclodextrin matrix solid-phase micro-extraction head - Google Patents
Manufacturing method of beta-cyclodextrin matrix solid-phase micro-extraction head Download PDFInfo
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- CN102008945A CN102008945A CN 201010253173 CN201010253173A CN102008945A CN 102008945 A CN102008945 A CN 102008945A CN 201010253173 CN201010253173 CN 201010253173 CN 201010253173 A CN201010253173 A CN 201010253173A CN 102008945 A CN102008945 A CN 102008945A
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Abstract
The invention relates to a manufacturing method of a beta-cyclodextrin matrix solid-phase micro-extraction head, belonging to the trace analysis field of volatile and semi-volatile organic matter in foods, environment and biological samples. The manufacturing method comprises the following steps of: (1) selecting and pretreating quartz fiber; (2) manufacturing the solid-phase micro-extraction head: preparing a sol from a coating material containing polydimethylsiloxane and beta-cyclodextrin, placing the quartz fiber treated in the step (1) in the sol, taking out, gelling at room temperature, aging by heating and refluxing the aged gel by using dichloromethane to manufacture the solid-phase micro-extraction head. In the invention, the beta-cyclodextrin and the polydimethylsiloxane are combined and used as the solid-phase micro-extraction coating material to manufacture the extraction head, and the extraction head enlarges the selection range of a coating on the polarity of an absorbed substance and is especially applicable to the detection of organic matter such as phenols and the like in perfume compositions and environment water samples and the detection of residual pesticides in fruits and vegetables.
Description
Technical field
The invention belongs to the trace analysis field of volatility and semi-volatile organic matter, the trace analysis method that particularly relates to volatility and semi-volatile organic matter in food, environment, the biological sample, particularly, the present invention relates to a kind of preparation method of beta-schardinger dextrin-matrix solid phase micro-extraction extraction head.
Background technology
Solid phase micro-extraction technique (SPME) is the sample pre-treatments and the beneficiation technologies of a novelty of the rise nineties in 20th century, it developed research by the Pawliszyn professor's of Canadian Waterloo university research group in 1989 at first first, belonged to non-solvent selective extraction method.
Solid phase micro-extraction technique almost can be used for the analysis of all kinds of volatility of sample such as gas, liquid, biology, solid or half volatile material.The maximum characteristics of SPME integrate sampling, extraction, enrichment, sample introduction exactly, thereby it is easy and simple to handle, and do not need solvent, rate of extraction is fast, running cost is low, free from environmental pollution, be convenient to realize automation and be easy to efficiently separate the detection means coupling with chromatogram, electrophoresis etc., therefore, in chemistry, medicine, food, environmental area and Pharmaceutical Analysis, obtained using widely.
The at present commercial coating that is used to prepare micro-extraction extraction head has dimethyl silicone polymer (PDMS, 7,30,100 μ m); Polyacrylate (PA, 85 μ m); Dimethyl silicone polymer/divinylbenzene (PDMS/DVB, 60,65 μ m); Dimethyl silicone polymer/carboxyethyl (PDMS/CAR, 75,85 μ m); Divinylbenzene/carboxyethyl (DVB/CAR, 30,50 μ m); Polyethylene glycol/divinylbenzene (CW/DVB, 65,70 μ m); Polyethylene glycol/template resin (CW/TPR, 50 μ m); Divinylbenzene/carboxyethyl/dimethyl silicone polymer (DVB/CAR/PDMS, 30,50 μ m).Commodity coating kind is limited, and selectivity is relatively poor, and costs an arm and a leg, thereby has limited its range of application greatly, and therefore many researchers are devoted to the research of new coating material.
Summary of the invention
It is few that the present invention overcomes in the prior art solid-phase micro-extraction coating kind, the prepared narrow problem of extracting head range of application, the preparation method of a kind of beta-schardinger dextrin-matrix solid phase micro-extraction extraction head (hereinafter referred extracting head) is provided, this method utilize beta-schardinger dextrin-in conjunction with dimethyl silicone polymer as solid-phase micro-extraction coating material preparation extracting head, the extracting head of preparing has enlarged the range of choice of coating to adsorbed material polarity, be specially adapted to fragrance form, Determination of Residues Pesticide in organic matter such as phenols and the fruits and vegetables in the environmental water sample.
Technical scheme of the present invention is:
Concrete, the invention provides a kind of preparation method of beta-schardinger dextrin-matrix solid phase micro-extraction extraction head, this method is used beta-schardinger dextrin-in conjunction with the solid-phase micro-extraction coating of dimethyl silicone polymer as extracting head.
The present invention also provides a kind of preparation method of beta-schardinger dextrin-matrix solid phase micro-extraction extraction head, this method is used beta-schardinger dextrin-in conjunction with the solid-phase micro-extraction coating of dimethyl silicone polymer as extracting head, uses the matrix that quartz fibre applies as solid-phase micro-extraction coating.
Concrete, the preparation method of above-mentioned extracting head comprises the steps:
(1) preliminary treatment of quartz fibre;
(2) making of extracting head: the coating material that will comprise dimethyl silicone polymer and beta-schardinger dextrin-is made colloidal sol, with the quartz fibre that step (1) was handled, place the colloidal sol back to take out, become glue under the room temperature, it is aging to heat up, and makes solid phase micro-extraction extraction head with methylene chloride reflux after aging the finishing.
Particularly, among the preparation method of above-mentioned extracting head, the length of preferred quartz fibre is 10-40mm, and diameter is 0.05-2mm.
Preferably, the preliminary treatment of described quartz fibre is meant quartz fibre dichloromethane solution immersion treatment, to remove protective polyamide layer, uses hydrogen fluoride etch 10-60min again, and is extremely neutral with deionized water rinsing at last, flows down oven dry at 120-150 ℃ of nitrogen.
Preferably, among the preparation method of above-mentioned extracting head, described step (2) is:
Get hydroxy-end capped dimethyl silicone polymer, with carrene dilution dissolving, add beta-schardinger dextrin-, containing hydrogen silicone oil, trifluoroacetic acid and raw material X, stir, make colloidal sol, described raw material X is the mixture of epoxypropoxy trimethyl silane and tetraethoxysilane, or be MTMS, the quartz fibre that to handle through step (1) takes out after placing colloidal sol 20-60min, becomes glue 10-24h under the room temperature, it is aging to carry out temperature programming again, aging finishing is placed in the middle of the cable type extractor according, in 30-60 ℃ of backflow 1-4h, makes solid phase micro-extraction extraction head with carrene.
Preferably, among the preparation method of above-mentioned extracting head, the aging process of described intensification is under nitrogen protection, and 100-150 ℃ keeps 2-4h, and 150-180 ℃ keeps 2-4h, and 200-240 ℃ keeps 30-60min then, promptly finishes aging.
Preferably, among the preparation method of above-mentioned extracting head, wherein the addition ratio of dimethyl silicone polymer, beta-schardinger dextrin-, containing hydrogen silicone oil, trifluoroacetic acid and raw material X is
Dimethyl silicone polymer 1mg
Beta-schardinger dextrin-0.2-0.5mg
Containing hydrogen silicone oil 0.16-0.5mg
Trifluoroacetic acid 0.14-0.5 μ l
Raw material X 0.16-0.5 μ l
Described raw material X is the mixture of epoxypropoxy trimethyl silane and tetraethoxysilane, or is MTMS.
Preferably, among the preparation method of above-mentioned extracting head, described raw material X is the mixture of epoxypropoxy trimethyl silane and tetraethoxysilane, and the volume ratio of epoxypropoxy trimethyl silane and tetraethoxysilane is 0.5-5: 1.
Adopting the coating layer thickness of the extracting head of above-mentioned preparation method's preparation is 10-100 μ m.
The beneficial effect that the present invention had is:
The present invention utilize beta-schardinger dextrin-in conjunction with dimethyl silicone polymer as solid-phase micro-extraction coating material preparation extracting head, this extracting head is by the special cavity structure of beta-schardinger dextrin-, interior hydrophobic, outer hydrophilic, increased adsorption capacity to polar substances, in conjunction with the nonpolar feature of dimethyl silicone polymer, thereby enlarged the range of choice of coating to adsorbed material polarity.Be specially adapted to fragrance form, Determination of Residues Pesticide in organic matter such as phenols and the fruits and vegetables in the environmental water sample.
Description of drawings:
Fig. 1 is not for adopting the gas-chromatography baseline chart of extracting head;
Fig. 2 is for adopting the gas-chromatography baseline chart of extracting head under desorption condition of the present invention's preparation;
Fig. 3 is the gas chromatogram of the extracting head separating phenols material of employing embodiment 1 preparation.
Among Fig. 3,1 is phenol, and 2 is the 2-methylphenol, and 3 is 2, the 4-xylenol, and 4 is 2, the 4-chlorophenesic acid.
Adopt the equal glitch-free baseline that can produce as shown in Figure 2 of arbitrary extracting head of the method for the invention preparation, comparison diagram 1 and Fig. 2 under desorption condition, can cause the fixedly loss of phase coating as can be seen hardly; As can be seen from Figure 3, the extracting head of the method for the invention preparation has extraction efficiency preferably for polarity than large compound, has remedied the deficiency that commercial PDM S extracting head is applicable to apolar substance, has widened SBSE The Application of Technology scope.
The specific embodiment
The invention will be further described below in conjunction with drawings and the specific embodiments.
The preparation method of embodiment 1 beta-schardinger dextrin-matrix solid phase micro-extraction extraction head:
(1), choosing and preliminary treatment of quartz fibre:
Choose long 20mm, diameter is the quartz fibre of 0.1mm, utilizes the dichloromethane solution immersion treatment, to remove protective polyamide layer, uses hydrogen fluoride etch 10min again, spend at last from water flushing to neutral, flow down oven dry at 120 ℃ of nitrogen;
(2), the making of solid phase micro-extraction extraction head:
Get the 400mg hydroxyl endblocked polydimethylsiloxane; dilute with 600 μ l carrene; add the 130mg beta-schardinger dextrin-; the 100mg containing hydrogen silicone oil; 100 μ l MTMSs and 100 μ l trifluoroacetic acids; stir; make colloidal sol, the quartz fibre that will handle through step (1) takes out after placing colloidal sol 30min; become glue 12h under the room temperature; under nitrogen protection, it is aging to carry out temperature programming, and 120 ℃ keep 3h; 180 ℃ keep 3h; 240 ℃ keep 60min then, promptly finish agingly, and aging finishing is placed in the middle of the cable type extractor according; in 40 ℃ of backflow 2h, make solid phase micro-extraction extraction head with carrene.
The preparation method of embodiment 2 beta-schardinger dextrin-matrix solid phase micro-extraction extraction heads:
(1), choosing and preliminary treatment of quartz fibre:
Choose long 20mm, diameter is the quartz fibre of 0.1mm, utilizes the dichloromethane solution immersion treatment, to remove protective polyamide layer, uses hydrogen fluoride etch 10min again, and is extremely neutral with deionized water rinsing at last, flows down oven dry at 120 ℃ of nitrogen;
(2); the making of solid phase micro-extraction extraction head: get the hydroxy-end capped dimethyl silicone polymer of 400mg; dilute with 600 μ l carrene; add the 130mg beta-schardinger dextrin-; the 100mg containing hydrogen silicone oil; the tetraethoxysilane of 50 μ l epoxypropoxy trimethyl silanes and 50 μ l and 100 μ l trifluoroacetic acids; stir; make colloidal sol; the quartz fibre that to handle through step (1); take out after placing colloidal sol 30min; become glue 12h under the room temperature; under nitrogen protection, it is aging to carry out temperature programming, and 120 ℃ keep 3h; 180 ℃ keep 3h; 240 ℃ keep 60min then, promptly finish agingly, and aging finishing is placed in the middle of the cable type extractor according; in 40 ℃ of backflow 2h, make solid phase micro-extraction extraction head with carrene.
The preparation method of embodiment 3 beta-schardinger dextrin-matrix solid phase micro-extraction extraction heads:
(1), choosing and preliminary treatment of quartz fibre: choose long 20mm, diameter is the quartz fibre of 0.1mm, utilizes the dichloromethane solution immersion treatment, to remove protective polyamide layer, use hydrogen fluoride etch 10min again, extremely neutral with deionized water rinsing at last, flow down oven dry at 135 ℃ of nitrogen;
(2); the making of solid phase micro-extraction extraction head: get the hydroxy-end capped dimethyl silicone polymer of 400mg; dilute with 600 μ l carrene; add the 170mg beta-schardinger dextrin-; the 120mg containing hydrogen silicone oil; 90 μ l MTMSs and 110 μ l trifluoroacetic acids; stir; make colloidal sol; the quartz fibre that to handle through step (1); take out after placing colloidal sol 40min; become glue 12h under the room temperature; under nitrogen protection, it is aging to carry out temperature programming, and 120 ℃ keep 3h; 180 ℃ keep 4h; 240 ℃ keep 30min then, promptly finish agingly, and aging finishing is placed in the middle of the cable type extractor according; in 45 ℃ of backflow 2h, make solid phase micro-extraction extraction head with carrene.
The preparation method of embodiment 4 beta-schardinger dextrin-matrix solid phase micro-extraction extraction heads:
(1), choosing and preliminary treatment of quartz fibre: choose long 20mm, diameter is the quartz fibre of 0.1mm, utilizes the dichloromethane solution immersion treatment, to remove protective polyamide layer, use hydrogen fluoride etch 10min again, extremely neutral with deionized water rinsing at last, flow down oven dry at 150 ℃ of nitrogen;
(2); the making of solid-phase micro-extraction fibre: get the hydroxy-end capped dimethyl silicone polymer of 400mg; dilute with 600 μ l carrene; add the 130mg beta-schardinger dextrin-; the 110mg containing hydrogen silicone oil; 130 μ l MTMSs and 90 μ l trifluoroacetic acids; stir; make colloidal sol; the quartz fibre that to handle through step (1); take out after placing colloidal sol 30min; become glue 12h under the room temperature; under nitrogen protection, it is aging to carry out temperature programming, and 120 ℃ keep 3.5h; 180 ℃ keep 3h; 200 ℃ keep 60min then, promptly finish agingly, and aging finishing is placed in the middle of the cable type extractor according; in 40 ℃ of backflow 2h, make solid phase micro-extraction extraction head with carrene.
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 (9)
1. the preparation method of a beta-schardinger dextrin-matrix solid phase micro-extraction extraction head is characterized in that: this method is used beta-schardinger dextrin-in conjunction with the coating material of dimethyl silicone polymer as the solid-phase micro-extraction coating of extracting head.
2. preparation method according to claim 1 is characterized in that: this method is used the matrix that quartz fibre applies as solid-phase micro-extraction coating.
3. preparation method according to claim 1 and 2 is characterized in that: this method comprises the steps:
(1) preliminary treatment of quartz fibre;
(2) making of extracting head: the coating material that will comprise dimethyl silicone polymer and beta-schardinger dextrin-is made colloidal sol, with the quartz fibre that step (1) was handled, place the colloidal sol back to take out, become glue under the room temperature, it is aging to heat up, and makes solid phase micro-extraction extraction head with methylene chloride reflux after aging the finishing.
4. preparation method according to claim 3 is characterized in that: the length of described quartz fibre is 10-40mm, and diameter is 0.05-2mm.
5. preparation method according to claim 3; it is characterized in that: the preliminary treatment of described quartz fibre is meant quartz fibre dichloromethane solution immersion treatment; to remove protective polyamide layer; use hydrogen fluoride etch 10-60min again; extremely neutral with deionized water rinsing at last, flow down oven dry at 120-150 ℃ of nitrogen.
6. preparation method according to claim 3 is characterized in that: described step (2) is:
Get hydroxyl endblocked polydimethylsiloxane, with carrene dilution dissolving, add beta-schardinger dextrin-, containing hydrogen silicone oil, trifluoroacetic acid and raw material X, stir, make colloidal sol, described raw material X is the mixture of epoxypropoxy trimethyl silane and tetraethoxysilane, or be MTMS, the quartz fibre that to handle through step (1) takes out after placing colloidal sol 20-60min, becomes glue 10-24h under the room temperature, it is aging to carry out temperature programming again, aging finishing is placed in the middle of the cable type extractor according, in 30-60 ℃ of backflow 1-4h, makes solid phase micro-extraction extraction head with carrene.
7. preparation method according to claim 6 is characterized in that: the aging process of described intensification is under nitrogen protection, and 100-150 ℃ keeps 2-4h, and 150-180 ℃ keeps 2-4h, and 200-240 ℃ keeps 30-60min then, promptly finishes aging.
8. preparation method according to claim 6 is characterized in that: wherein the addition ratio of dimethyl silicone polymer, beta-schardinger dextrin-, containing hydrogen silicone oil, trifluoroacetic acid and raw material X is
Dimethyl silicone polymer 1mg
Beta-schardinger dextrin-0.2-0.5mg
Containing hydrogen silicone oil 0.16-0.5mg
Trifluoroacetic acid 0.14-0.5 μ l
Raw material X 0.16-0.5 μ l
Described raw material X is the mixture of epoxypropoxy trimethyl silane and tetraethoxysilane, or is MTMS.
9. method according to claim 8 is characterized in that: raw material X is the mixture of epoxypropoxy trimethyl silane and tetraethoxysilane, and wherein the volume ratio of epoxypropoxy trimethyl silane and tetraethoxysilane is 0.5-5: 1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107607611A (en) * | 2017-09-06 | 2018-01-19 | 大连工业大学 | A kind of high resolution mass spec analysis method using SPE direct injected |
| JPWO2017135068A1 (en) * | 2016-02-03 | 2018-11-29 | ゲステル株式会社 | Organic component extraction element |
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2010
- 2010-08-12 CN CN 201010253173 patent/CN102008945A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2017135068A1 (en) * | 2016-02-03 | 2018-11-29 | ゲステル株式会社 | Organic component extraction element |
| JP7004298B2 (en) | 2016-02-03 | 2022-02-10 | ゲステル株式会社 | Element for extracting organic components |
| CN107607611A (en) * | 2017-09-06 | 2018-01-19 | 大连工业大学 | A kind of high resolution mass spec analysis method using SPE direct injected |
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Application publication date: 20110413 |