CN104258597B - A kind of Phen modify organic-silica gel hybridization capillary tube monolithic column - Google Patents
A kind of Phen modify organic-silica gel hybridization capillary tube monolithic column Download PDFInfo
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- CN104258597B CN104258597B CN201410517030.XA CN201410517030A CN104258597B CN 104258597 B CN104258597 B CN 104258597B CN 201410517030 A CN201410517030 A CN 201410517030A CN 104258597 B CN104258597 B CN 104258597B
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Abstract
The invention discloses that a kind of Phen modifies organic-silica gel hybridization capillary tube monolithic column and application thereof, be take Phen as ionic liquid, modify obtained described integral post through pretreatment, the preparation of post bed, post bed.The positively charged ion-exchange site that can provide of Phen, there is the pyridine ring of large pi-conjugated system simultaneously and symmetrical configuration, with its prepare organic-silica gel hybridization capillary tube monolithic column has the multi-acting forces such as π-π interacts, hydrogen bond action and electrostatic interaction, can reach good separating effect; Simultaneously, integral post prepared by the present invention had both eliminated the troublesome operation such as traditional packed column filling, and the problem such as the bubble generation that causes of sintering stopper, overcome again open tubular column capacity low, compare little shortcoming, its stable in properties, favorable reproducibility, can use within the scope of larger pH, its EOF size can control by regulating the pH of mobile phase, and Pyrogentisinic Acid's class and aniline category matter have good separating effect.
Description
Technical field
The invention belongs to capillary chromatographic column technical field, be specifically related to that a kind of Phen modifies organic-silica gel hybridization capillary tube monolithic column and application thereof.
Background technology
Capillary electric chromatogram be the one that in recent years grows up in electrophoretic techniques and high performance liquid chromatography basis efficiently, novel Micro-Column Separation method fast.As the important component part of electrochromatography isolation technics, capillary electric chromatographic column can be divided into open tubular column, packed column and integral post, wherein capillary monolithic column overcomes open tubular column and compares not enough shortcoming, avoid the step that packed column need make stopper simultaneously, have and prepare simple, good penetrability, post effect advantages of higher.
Ionic liquid (IL) is relatively large by molecular weight, the asymmetrical organic cation of structure and less inorganic anion form, having the advantages such as fusing point low (be generally less than or equal 100 DEG C), high and in organic or inorganic solution the dissolubility of stability are good, is a class novel medium or " soft " functional material (softmaterials) of being worth research.(the Analyticachimicaacta.2012 such as Wang, 712 (27): 1-8) 1-vinyl-3-octylimidazole villaumite and dodecyl methyl acrylate (LMA) are caused free radicals copolymerization reaction by heat and prepare a novel overall post, not only can at larger pH(2.0-12.0) produce reverse EOF in scope, effectively can also eliminate the absorption of capillary wall to alkali compounds, have good effect to Separation of Neutral and charging cpd, this is also that reported first prepares Organic Polymer Monolithic Columns ionic liquid as function monomer.(the JournalofChromatographyA such as merchant, 2011,1218 (22): 3459-3465) functional silica gel integral post is prepared by chemical bonding N-methylimidazole ionic liquid, apply multi-acting forces such as comprising π-π interaction, hydrogen bond action and electrostatic interaction, successfully achieving the mixing of multiple separation mechanism exists on same splitter, effectively can be separated the compound of the number of different types such as inorganic ions, phenol, benzoic acids, alkylbenzene.(the JournalofChromatographyA such as Han, 2003,985 (1-2): 447-454) successfully N-methylimidazole is modified in organic-silica gel hybridization integral post, because it produces reverse EOF at acidic phs, typical reverse-phase chromatography pattern is presented to the separation of four kinds of aromatic hydrocarbon, also can be separated seven kinds of inorganic anions simultaneously.Phen contains two pyridine rings, can provide a large amount of ion-exchange sites.At present, Phen, as a kind of new ionic liquid, there is no the relevant report for organic-silica gel hybridization post.
Summary of the invention
The object of the present invention is to provide a kind of Phen to modify organic-silica gel hybridization capillary tube monolithic column and application thereof, this organic-silica gel hybridization capillary tube monolithic column had both eliminated the complicated loaded down with trivial details operations such as traditional packed column filling, and the problem such as the bubble generation that causes of sintering stopper, overcome again open tubular column capacity low, compare little shortcoming, its stable chemical nature, favorable reproducibility, has more action site with sample, and Pyrogentisinic Acid's class and aniline category matter have good separating effect.
For achieving the above object, the present invention adopts following technical scheme:
Phen modify organic-silica gel hybridization capillary tube monolithic column, take Phen as ionic liquid, through pretreatment, the preparation of post bed, post bed modify obtained described organic-silica gel hybridization capillary tube monolithic column.
Its preparation method comprises the steps:
1) pretreatment: get suitable length capillary column, successively after water flowing 0.5h, 1M hydrochloric acid 1h, water 0.5h, 1M NaOH 0.5h, clogs two ends in 100 DEG C of reaction 3h; Water flowing 0.5h, 0.1M hydrochloric acid 0.5h, water 0.5h, methyl alcohol 0.25h, acetone 0.25h again, then 180 DEG C of nitrogen blow 3h;
2) post bed preparation: polyethylene glycol and urea are dissolved in 0.01mol/L acetum, being stirred to dissolve completely is placed in 0 DEG C of ice bath, dropwise add tetramethoxy-silicane and r-chloropropyl trimethoxyl silane, vigorous stirring 4h, obtain transparent homogeneous collosol intermixture; Inject the good capillary of pretreatment by after collosol intermixture ultrasonic vibration 5min, by capillary sealing two ends, in 55 DEG C of water-baths, react 12h, then use redistilled water and washed with methanol respectively, obtain chloropropyl-silica gel hybridization capillary tube monolithic column;
3) post bed is modified: by containing after the methanol aqueous solution ultrasonic process 5min of Phen and sodium iodide, the capillary that injection prepares, 80 DEG C of water-bath 12h, then uses redistilled water and washed with methanol respectively, obtain after modification organic-silica gel hybridization capillary tube monolithic column.
Described methanol aqueous solution is that wherein the concentration of Phen is 30-60mg/mL, and the concentration of sodium iodide is 10mg/mL by the 1:1 mixing by volume of first alcohol and water.
Described Phen modify organic-silica gel hybridization capillary tube monolithic column changes its EOF size by the salinity and pH value regulating organic phase, buffer salt, can be used for Separation of Benzene phenols and aniline category matter.
Remarkable advantage of the present invention is:
(1) the present invention utilizes Phen to modify organic-silica gel hybridization capillary tube monolithic column, due to the positively charged ion-exchange site that can provide of Phen, there is the pyridine ring of large pi-conjugated system simultaneously and symmetrical configuration, there is by the integral post that it is prepared the multi-acting forces such as π-π interaction, hydrogen bond action and electrostatic interaction, can separating effect be improved.
(2) organic-silica gel hybridization capillary tube monolithic column that the present invention utilizes Phen to modify, both the complicated loaded down with trivial details operations such as traditional packed column filling had been eliminated, and the problem such as the bubble generation that causes of sintering stopper, overcome again open tubular column capacity low with compare little shortcoming, there is property and structure stablize, the advantage of favorable reproducibility.
Accompanying drawing explanation
Fig. 1 be chloropropyl-silica gel hybridization capillary capillary monolithic column (post A) and Phen modify organic-silica gel hybridization capillary tube monolithic column (post B) in the mobile phase of different pH value on the impact of EOF.
Fig. 2 be Phen modify organic-silica gel hybridization capillary tube monolithic column in the graph of a relation of different ethane nitrile content and four Small molecular retention factors.
Fig. 3 be Phen modify organic-silica gel hybridization capillary tube monolithic column in the graph of a relation of different ethane nitrile content and 5 kinds of phenol compound retention factors.
Fig. 4 be Phen modify organic-silica gel hybridization capillary tube monolithic column in the graph of a relation of different ethane nitrile content and 4 kinds of amino benzenes compounds retention factors.
Detailed description of the invention
More being convenient to make content of the present invention understand, below in conjunction with detailed description of the invention, technical solutions according to the invention are described further, but the present invention being not limited only to this.
Embodiment 1
1) pretreatment: get some identical capillary columns, respectively successively after water flowing 0.5h, 1M hydrochloric acid 1h, water 0.5h, 1M NaOH 0.5h, clogs two ends in 100 DEG C of reaction 3h; Water flowing 0.5h, 0.1M hydrochloric acid 0.5h, water 0.5h, methyl alcohol 0.25h, acetone 0.25h again, then 180 DEG C of nitrogen blow 3h;
2) post bed preparation: 660mg polyethylene glycol and 900mg urea are placed in round bottom beaker, add in 5.0mL0.01mol/L acetum, being stirred to dissolve completely is placed in 0 DEG C of ice bath, dropwise add 1800 μ L tetramethoxy-silicanes and 600 μ L r-chloropropyl trimethoxyl silanes, vigorous stirring 4h, obtains transparent homogeneous collosol intermixture; Pipette 1.0mL collosol intermixture, ultrasonic vibration 5min in centrifuge tube, then be injected in the good capillary of pretreatment respectively, by capillary sealing two ends, in 55 DEG C of water-baths, react 12h, then use redistilled water and washed with methanol, obtain chloropropyl-silica gel hybridization capillary tube monolithic column (post A);
3) post bed is modified: dissolve in methanol-water (1:1, v/v) mixed solution by 60mg/mL Phen and 10mg/mL sodium iodide, ultrasonic process 5min obtains Phen solution; Get part chloropropyl-silica gel hybridization capillary tube monolithic column, inject gained Phen solution respectively, 80 DEG C of water-bath 12h, then use redistilled water and washed with methanol respectively, obtain that Phen modifies organic-silica gel hybridization capillary tube monolithic column (post B).
The Phen that obtains with the present embodiment modify organic-silica gel hybridization capillary tube monolithic column (internal diameter 75 μm, overall length 55cm, effective length 35cm) measures mobile phase pH impact on EOF within the scope of 3-9, result is as Fig. 1; Condition determination is: 50% phosphoric acid triethylamine buffer solution (pH7.0,10mmol/L)-50% acetonitrile is mobile phase, separation voltage+20kV, determined wavelength 214nm, flow velocity 0.1mL/min, and pressure 3.4MPa, using thiocarbamide as electroendosmotic flow marker; With obtained chloropropyl-silica gel hybridization capillary tube monolithic column for contrast, its separation voltage-20kV, other conditions are identical.
Embodiment 2
With the Phen that embodiment 1 is obtained modify organic-silica gel hybridization capillary tube monolithic column, measure the relation (condition determination is with embodiment 1) of different ethane nitrile content (ethane nitrile content is 40%-98%) and four Small molecular (toluene, dimethyl formamide, formamide, thiocarbamide) retention factors in mobile phase, result is as Fig. 2.
As can be seen from Figure 2, when ethane nitrile content is greater than 90%, the present embodiment hybridization capillary tube monolithic column presents hydrophilic retention mechanism.
Embodiment 3
With the Phen that embodiment 1 is obtained modify organic-silica gel hybridization capillary tube monolithic column, measure the relation of different ethane nitrile content and 5 kinds of phenol compound (phloroglucin, hydroquinones, resorcinol, catechol, phenol) retention factors, result is as Fig. 3; Wherein phosphoric acid triethylamine buffer solution is pH7.0,1.0mmol/L, and ethane nitrile content is 10%-30%, separation voltage-20kV, and all the other condition determinations are with embodiment 1.
As can be seen from Figure 3, raise with ethane nitrile content, the retention factors of 5 kinds of phenol compounds decreases, and the present embodiment hybridization capillary tube monolithic column shows as typical anti-phase retention mechanism.
Embodiment 4
With the Phen that embodiment 1 is obtained modify organic-silica gel hybridization capillary tube monolithic column, measure the relation of different ethane nitrile content and 4 kinds of amino benzenes compounds (sulfanilamide (SN), diphenylamines, ortho-nitraniline, alpha naphthylamine) retention factors, result is as Fig. 4; Wherein phosphoric acid triethylamine buffer solution is pH7.0,3.0mmol/L, and ethane nitrile content is 30%-70%, separation voltage-20kV, and all the other condition determinations are with embodiment 1.
As can be seen from Figure 4, raise with ethane nitrile content, the retention factors of 4 kinds of amino benzenes compounds decreases, and the present embodiment hybridization capillary tube monolithic column shows as typical anti-phase retention mechanism.
The foregoing is only preferred embodiment of the present invention, all equalizations done according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (2)
1. organic-silica gel hybridization capillary tube monolithic column that Phen is modified, is characterized in that: take Phen as ionic liquid, through pretreatment, the preparation of post bed, post bed modify obtained described organic-silica gel hybridization capillary tube monolithic column;
Described post bed preparation is first dissolved in 0.01mol/L acetum by polyethylene glycol and urea, being stirred to dissolve completely is placed in 0 DEG C of ice bath, dropwise add tetramethoxy-silicane and r-chloropropyl trimethoxyl silane, vigorous stirring 4h, obtain transparent homogeneous collosol intermixture; Inject the good capillary of pretreatment by after gained collosol intermixture ultrasonic vibration 5min, by capillary sealing two ends, in 55 DEG C of water-baths, react 12h, then use redistilled water and washed with methanol respectively;
It is first by after the methanol aqueous solution ultrasonic process 5min containing Phen and sodium iodide that described post bed is modified, inject the capillary prepared, 80 DEG C of water-bath 12h, then use redistilled water and washed with methanol respectively, obtain after modification organic-silica gel hybridization capillary tube monolithic column.
2. according to claim 1 Phen modify organic-silica gel hybridization capillary tube monolithic column, it is characterized in that: described methanol aqueous solution is by the 1:1 mixing by volume of first alcohol and water, wherein the concentration of Phen is 30-60mg/mL, and the concentration of sodium iodide is 10mg/mL.
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| CN107297201B (en) * | 2016-04-14 | 2020-07-14 | 中国石油化工股份有限公司 | 4, 5-imidazole dicarboxylic acid modified organic-silica gel hybrid monolithic column and application |
| CN107297087B (en) * | 2016-04-14 | 2020-05-08 | 中国石油化工股份有限公司 | Histidine-modified organic-silica gel hybrid monolithic column and preparation method and application thereof |
| CN113419003B (en) * | 2021-06-18 | 2023-06-16 | 安徽师范大学 | Multi-channel open-pipe silica gel capillary column taking metal filaments as templates and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2300597A1 (en) * | 1975-02-14 | 1976-09-10 | Erap | Treating silica alumina chromatographic supports - with basic organic cpd. to remove catalytic activity |
| JPS61204562A (en) * | 1985-03-07 | 1986-09-10 | Asahi Chem Ind Co Ltd | Adsorbent for optical resolution |
| CN101927182A (en) * | 2010-07-05 | 2010-12-29 | 北京林业大学 | Biodiesel catalyst and method for preparing biodiesel by using same |
| CN103111263A (en) * | 2013-02-05 | 2013-05-22 | 中山大学 | Metallic-organic gel matrix solid-phase microextraction head with multiple levels of hole channels and preparation method thereof |
| CN103550954A (en) * | 2013-11-14 | 2014-02-05 | 福州大学 | Phenylimidazole ionic liquid-silica gel hybrid capillary tube monolithic column |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2300597A1 (en) * | 1975-02-14 | 1976-09-10 | Erap | Treating silica alumina chromatographic supports - with basic organic cpd. to remove catalytic activity |
| JPS61204562A (en) * | 1985-03-07 | 1986-09-10 | Asahi Chem Ind Co Ltd | Adsorbent for optical resolution |
| CN101927182A (en) * | 2010-07-05 | 2010-12-29 | 北京林业大学 | Biodiesel catalyst and method for preparing biodiesel by using same |
| CN103111263A (en) * | 2013-02-05 | 2013-05-22 | 中山大学 | Metallic-organic gel matrix solid-phase microextraction head with multiple levels of hole channels and preparation method thereof |
| CN103550954A (en) * | 2013-11-14 | 2014-02-05 | 福州大学 | Phenylimidazole ionic liquid-silica gel hybrid capillary tube monolithic column |
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