CN101091912A - Solid phase method for extracting elution reagent by using derivative of adamantine as supporter containing cyclodextrin of solid phase extraction - Google Patents
Solid phase method for extracting elution reagent by using derivative of adamantine as supporter containing cyclodextrin of solid phase extraction Download PDFInfo
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- CN101091912A CN101091912A CN 200710039942 CN200710039942A CN101091912A CN 101091912 A CN101091912 A CN 101091912A CN 200710039942 CN200710039942 CN 200710039942 CN 200710039942 A CN200710039942 A CN 200710039942A CN 101091912 A CN101091912 A CN 101091912A
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Abstract
The invention relates to a solid phase extract method of using the diamond alkyl ramification as elution reagent ingredient which contains link dextrin solid phase extract load body, belongs to the related separation enrichment chemistry and the solid phase extract processing of the chemical operation technology domain. The step of the invention method is as follow: (1) activating the solid phase extraction column which contains the link dextrin load body, flushing the extraction column by methyl alcohol or two distilled water; (2) taking the sample, joining the sample solution in the solid phase extraction column, and forcing the solution into the fixed phase, and keeping the sample analysis on the fixed phase; (3) drip washing, with two distilled water and so on drip washings, washing off the sample component which does not need or abbreviates this step; (4) eluting reagent which contains the diamond alkane ramification through the solid phase extraction column, and eluting the wait analysis from the link dextrin solid phase extract load body; (5) examination analysis, the eluent which collects from the above directly carries on chromatogram, electrophoresis and analyses, then computing and analyzing the obtained detection curve atlas, or the collection eluent uses in other research work.
Description
Technical field
The present invention relates to adopt adamantane derivative as the SPE method that contains the elution reagent of cyclodextrin SPE carrier, belong to the SPE technology field of relevant separation and concentration chemistry and chemical industry operation.
Background technology
SPE (SPE) is the novel extraction technology that occurs at the seventies, is mainly used in the preparation of analytical sample.SPE has following tangible advantages: simple, quick, supporting SPE unit has shortened analysis time widely, and the sample of handling is easy to storage and transportation, is convenient to carry out quality control in different laboratories: be difficult for emulsification; Be applicable to the small samples processing; Do not need a large amount of high-purity, easy right, toxic solvents; Alternative adsorbent and type of solvent are a lot, and the kinds of experiments approach can be provided; Reduce and molten use and expose, guarantee experiment safety; Be easy to and the Other Instruments coupling, be implemented in line analysis; Low operation cost.SPE is widely used in environmental analysis, Pharmaceutical Analysis, clinical analysis and food and drink analysis, especially when processing environment and Biosample, best embodies the characteristics of this technology.Cyclodextrin is a kind of host molecule, it is introduced the material that can obtain having special absorption property in the solid carrier, such as being grafted to it on polymer backbone by coupling agent or applying modification or bonding on polymer and silica matrix.
Cyclodextrin (CD) is the cyclic oligomer sugar compounds that a class is linked by 6～12 glucose molecules, have the ability that forms inclusion compound with multiple compound because of its specific molecule structure makes it, thereby in fields such as medicine food, chemical industry and agricultural, be widely used.Wherein the most frequently used is beta-schardinger dextrin-, the cyclic oligosaccharide that it is made up of 7 glucose molecules.Because it has hydrophobic cavity, beta-schardinger dextrin-can be optionally interaction and some molecule by Subjective and Objective be combined into complex.Cyclodextrin can be used as optionally SPE carrier, realizes separation, enrichment etc. to some compound.The elution reagent that SPE is commonly used mostly is organic solvents such as methyl alcohol, acetonitrile at present.Because some compound of the inclusion effect of cyclodextrin adopts effectively wash-out of common organic eluting solvent such as methyl alcohol, acetonitrile.
Adamantane (adamantane) chemical name three ring [3.3.1.1] decane, molecular formula C
10H
16, be that the thiacyclohexane by three chair conformations condenses the cage shape hydrocarbon that forms, its structure height symmetry, highly stable.Owing to have specific structure and character, adamantane is a kind of emerging hot product of field of fine chemical, be the raw material of pharmacy, functional polymer, scenting cosmetics, sensitive photographic material, catalyst, surfactant and extraordinary lubriation material etc., have wide application prospects.This patent discloses the SPE method that adamantane derivative can be used as the novel elution reagent of SPE that contains cyclodextrin SPE carrier.
Adamantane can be represented its structure by following three kinds of forms:
Summary of the invention
The objective of the invention is to, contain cyclodextrin the SPE carrier extraction column in use, because the inclusion effect of cyclodextrin, some analyte or compound adopt effectively wash-out of common organic eluting solvent, for this reason, special proposition utilizes adamantane derivative as the SPE method that contains the novel elution reagent of SPE of cyclodextrin SPE carrier.
Adamantane derivative of the present invention is characterized in that having following process and step as the SPE method that contains the elution reagent of cyclodextrin SPE carrier:
A. contain the activation of the solid-phase extraction column of cyclodextrin SPE carrier
Wash extraction column with solvent methanol or with redistilled water,,, improve its reactivity to set up suitable SPE environment to purify fixedly phase cyclodextrin carrier;
B. go up sample
Sample solution is joined solid-phase extraction column gradually and forces sample solution to pass through fixedly phase, sample analytes is retained in fixing goes up mutually;
C. drip washing
After analyte obtained keeping, drip washing was fixing to wash unwanted sample component off or to omit this step;
D. wash-out
The elution reagent that will contain adamantane derivative then makes analysans elute from cyclodextrin SPE carrier by solid-phase extraction column;
E. check and analysis
The eluent that above-mentioned collection is obtained directly carry out analysis such as chromatogram, electrophoresis or collect under eluent be used for other research work.
Above-mentioned adamantane derivative elution reagent is for containing the derivative of adamantane structure in eluent, adamantane acid or amantadine are mixed with the elution reagent of desired concn; The adamantane acid elution reagent that uses is the adamantane acid elution reagent of 1-50mM, and it is the 1-adamantane acid to be dissolved in the NaOH of about 100mM use salt acid for adjusting pH value (7-12) obtained again.
Above-mentioned cyclodextrin includes alpha-cyclodextrin, beta-schardinger dextrin-, gamma-cyclodextrin and their derivative; The beta-schardinger dextrin-bonded silica gel is to contain a kind of in the cyclodextrin SPE carrier.
The advantage of the inventive method is:
(1) adamantane derivative comprises adamantane acid, amantadine etc., and is very strong with the inclusion effect of cyclodextrin, can be implemented in containing SPE when operation of cyclodextrin SPE carrier, carries out effective wash-out to combine stronger analyte with cyclodextrin; Other organic eluting solvents commonly used then can't be realized.
(2) adamantane derivative comprises adamantane acid, amantadine etc., and the solution behind its wash-out can directly carry out capillary electrophoresis analysis, need not specially treated, can realize fast detecting.
Description of drawings
Fig. 1 is the elution curve comparison diagram of acetonitrile and 1-adamantane acid wash-out 4-tert-butyl phenol.
Wherein: solid line partly is the elution curve of 50mM 1-adamantane acid;
Dotted portion is the elution curve of 40% acetonitrile;
Abscissa is the employed volume of elute soln; Ordinate is and the corresponding relative concentration with the detected 4-tert-butyl phenol of micellar electrokinetic chromatography method of elution volume.
Fig. 2 is the elution curve comparison diagram of acetonitrile and 1-adamantane acid wash-out bisphenol-A.
Wherein: solid line partly is the elution curve of 50mM 1-adamantane acid;
Dotted portion is the elution curve of 40% acetonitrile;
Abscissa is the employed volume of elute soln; Ordinate is and the corresponding relative concentration with the detected bisphenol-A of micellar electrokinetic chromatography method of elution volume.
Fig. 3 is for bisphenol-A and the 4-tert-butyl group-phenol does not pass through the solution (each 2mg/L) of SPE and the electrophoresis pattern after sample solution (each the 40 μ g/L) SPE contrasts.
Wherein: curve A is the electrophoresis pattern of bisphenol-A and the 4-tert-butyl group-phenol solution (each 2mg/L) that do not pass through SPE;
Curve B is the electrophoresis pattern after bisphenol-A and the 4-tert-butyl group-phenol sample solution (each the 40 μ m/L) SPE.
The ownership at peak is: No. 1 peak 4-tert-butyl group-phenol, No. 2 peak bisphenol-As, No. 3 peak 1-adamantane acids.
Abscissa is micellar electrokinetic chromatography detection time, and ordinate is the detected signal of corresponding micellar electrokinetic chromatography with the time.
The specific embodiment
After now the embodiments of the invention tool being described in.
The instrument and the experiment condition that are adopted in the present embodiment are as follows:
(1) HPCE, the HPCE system (CE-L1) for Singapore Pte company produces is equipped with UVIS 200 type UV-detectors, and data acquisition and processing (DAP) is finished by CSW chromatogram software.
(2) micellar electrokinetic chromatography (MEKC) process adopts above-mentioned Capillary Electrophoresis instrument.With the SDS of 25mM phosphate buffer (pH8.0) preparation 20mM, add 5% acetonitrile then, solution filters the back use through the filter of 0.45 micron pore size filter membrane, thereby obtains MECK cushioning liquid.Adopt pressure input mode (0.3psi), sample introduction 10s, separation voltage 20kV detects wavelength 214nm, 25 ℃ of experimental temperatures.
(3) (β-CD) is available from U.S. Sigma company for beta-schardinger dextrin-; Use the homemade beta-schardinger dextrin-bonded silica gel in this laboratory (CDS) in the present embodiment.
(4) CDS solid phase extraction column is by this laboratory self-control.
(5) sample solution adopts the mixed solution of the 4-tert-butyl group-phenol and bisphenol-A; This organic compound is to combine the analyte of formation inclusion complex and the compound that concentration and separation is treated in conduct with cyclodextrin.
(6) 50mM 1-adamantane acid is that the 1-adamantane acid is dissolved in the NaOH of 100mM, uses salt acid for adjusting pH value to 7 obtained again.
The specific operation process and the step of present embodiment are as follows:
(1) contains the activation of the solid-phase extraction column of cyclodextrin carrier
Successively,, improve its reactivity to set up suitable solid phase environment respectively with the methyl alcohol of 4ml and the redistilled water flushing extraction column of 4ml;
(2) go up sample
(a) mensuration of elution curve
With 10ml contain the 4-tert-butyl group-phenol and bisphenol-A respectively for the mixed solution of 2mg/L by solid-phase extraction column, the SPE carrier in this extraction column is the beta-schardinger dextrin-bonded silica gel; Force solution to pass through this and fixing extract carrier mutually, amalyzing substances in the solution is retained in fixingly goes up mutually.
(b) enrichment analytic process
By the extraction pillar, sample joins fixedly the phase extraction column and forces sample solution to pass through fixedly phase with 150mL sample solution (contain the 4-tert-butyl group-phenol, bisphenol-A each 40 μ g/L), and at this moment sample analytes is retained in to fix and goes up mutually.
(3) drip washing
After analyte obtains keeping, use fixedly phase of second distillation water wash, to wash unwanted component off.
(4) wash-out
Then with 50mM 1-adamantane acid (pH=7) eluting solvent and 5ml 40% methanol aqueous solution, the 40% acetonitrile solution wash-out solute respectively of solvent as a comparison, and obtain eluent, stand-by.
(5) check and analysis
The eluent that above-mentioned collection is obtained directly carries out analyses such as chromatogram, electrophoresis; This experiment check and analysis adopt above-mentioned micellar electrokinetic chromatography (MEKC) to carry out.
Test result is referring to the Fig. 1 in the accompanying drawing, Fig. 2 and Fig. 3.
Fig. 1 is the elution curve comparison diagram of acetonitrile and the 1-adamantane acid wash-out 4-tert-butyl group-phenol.
But the more 4-tert-butyl group-phenol under every milliliter of 1-adamantane acid elute soln wash-out as can be seen from the elution curve, the sample concentration under its corresponding wash-out is higher, represents that its elute effect is better than acetonitrile solvent.Solvent methanol then can't the wash-out 4-tert-butyl group-phenol in the test.
Fig. 2 is the elution curve comparison diagram of acetonitrile and 1-adamantane acid wash-out bisphenol-A.
But more bisphenol-A under every milliliter of 1-adamantane acid elute soln wash-out as can be seen from the elution curve, the sample concentration under its corresponding wash-out is higher, represents that its elute effect is better than acetonitrile solvent.Solvent methanol then can't the wash-out bisphenol-A in the test.
Fig. 3 is for bisphenol-A and the 4-tert-butyl group-phenol does not pass through the solution (each 2mg/L) of SPE and the electrophoresis pattern after sample solution (each the 40 μ) SPE contrasts.
Wherein: curve A is the electrophoresis pattern of bisphenol-A and the 4-tert-butyl group-phenol solution (each 2mg/L) that do not pass through SPE;
Curve B is the electrophoresis pattern after bisphenol-A and the 4-tert-butyl group-phenol sample solution (each the 40 μ m/L) SPE.
Abscissa is micellar electrokinetic chromatography detection time, and ordinate is the detected signal of corresponding micellar electrokinetic chromatography with the time.
Test shows, the sample solution that concentration is low contains bisphenol-A and each 40 μ m/L of the 4-tert-butyl group-phenol can obtain enrichment, the concentration enrichment of bisphenol-A is 1.44mg/L, the concentration enrichment of the 4-tert-butyl group-phenol is 1.40mg/L, and the solid phase extraction concentration multiple of bisphenol-A and the 4-tert-butyl group-phenol is respectively 36 and 35 (pressing peak height calculates).Test explanation SPE method of the present invention can play the purpose of enriched sample.
Claims (3)
1. adamantane derivative is characterized in that having following process and step as the SPE method that contains the elution reagent of cyclodextrin SPE carrier:
A. contain the activation of the solid-phase extraction column of Cyclodextrin carrier
Wash extraction column with solvent methanol or with redistilled water,,, improve its reactivity to set up suitable SPE environment to purify fixedly phase cyclodextrin carrier;
B. go up sample
Sample solution is joined solid-phase extraction column gradually and forces sample solution to pass through fixedly phase, sample analytes is retained in fixing goes up mutually;
C. drip washing
After analyte obtained keeping, drip washing was fixing to wash unwanted component off or to omit this step;
D. wash-out
The elution reagent that will contain adamantane derivative then makes analysans elute from cyclodextrin SPE carrier by solid-phase extraction column;
E. check and analysis
The eluent that above-mentioned collection is obtained directly carries out analysis such as chromatogram, electrophoresis or collects down that elute soln is used for other research work.
2. adamantane derivative as claimed in claim 1 is as the SPE method that contains the elution reagent of cyclodextrin SPE carrier, it is characterized in that described adamantane derivative elution reagent for contain the derivative of adamantane structure in eluent, derivatives such as adamantane acid or amantadine are mixed with the elution reagent of desired concn; The adamantane acid elution reagent that uses is the adamantane acid elution reagent of 1-50mM, and it is the 1-adamantane acid to be dissolved in the NaOH of about 100mM use salt acid for adjusting pH value to 7～12 obtained again.
3. adamantane derivative as claimed in claim 1 is characterized in that as the SPE method that contains the elution reagent of cyclodextrin SPE carrier described cyclodextrin includes alpha-cyclodextrin, beta-schardinger dextrin-, gamma-cyclodextrin and their derivative; The beta-schardinger dextrin-bonded silica gel is to contain a kind of in the cyclodextrin SPE carrier.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101565384B (en) * | 2008-12-23 | 2012-12-26 | 南开大学 | Cyclodextrin modified monolayer graphite, supramolecular complex thereof, preparation method and application |
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| CN101565384B (en) * | 2008-12-23 | 2012-12-26 | 南开大学 | Cyclodextrin modified monolayer graphite, supramolecular complex thereof, preparation method and application |
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Granted publication date: 20090902 Termination date: 20130425 |