CN102657952B - Hybrid-model capillary open-tubular chromatographic column and preparation method and applications thereof - Google Patents
Hybrid-model capillary open-tubular chromatographic column and preparation method and applications thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of a chromatographic column, in particular to a preparation method and applications of a hybrid-model capillary open-tubular chromatographic column. A stationary phase on the inner wall of the capillary open-tubular chromatographic column simultaneously has three kinds of functional groups, namely a group with positive charges, a group with negative charges and a hydrophobic group without charges. The preparation method comprises the following steps of: preparing a silicon source, a functional silicon source and ethanol into a hybrid solution according to different proportions, then adding a small amount of water and hydrochloric acid, heating and stirring at fixed temperature to obtain a sol; and coating the sol onto the inner wall of a open-tubular column to obtain the needed chromatographic column. The performance of the chromatographic column can be regulated by changing the proportions of synthesized raw materials. The direction and the size of electroosmotic flow of the prepared chromatographic column can be changed along with the change of the pH value of a flow phase. The chromatographic column can be used for separating aromatic compounds, acidic compounds, alkali compounds and the like of capillary electrochromatography.
Description
Technical field
The invention belongs to chromatographic technology field, be specifically related to a kind of mixed mode (rp mode-weak anionic switch mode) open-tubular capillary chromatographic column and its production and use.
Background technology
Along with the growing of capillary electrophoresis technique and the theoretical progress gradually of liquid chromatogram, emerge a kind of efficient micro-separate analytical technique, i.e. capillary electric chromatogram (CEC) technology fast.Owing to combining electrophoresis and chromatogram two kinds of mechanism, this technology has the high efficiency of Capillary Electrophoresis and the high selectivity of high performance liquid chromatography simultaneously, thus becomes a kind of novel Micro-Column Separation method.Because all separating behaviors complete in capillary inside entirely, the research of capillary column is a popular domain always, and it modifies with modification is the emphasis studied always.Different according to the existence form of Stationary liquid in capillary, capillary electric chromatogram can be divided three classes: electrochromatography, packed column electrochromatography, integral post electrochromatography.Wherein, open tubular column is simple due to preparation method, can eliminate joule heating effect, stopper effect and bubble effect etc. simultaneously, and become the focus of current research.
1992, El Rassi etc. by introduce with hydroxyl and season ammonia difunctional compound, prepared the surface modification capillary column that a kind of EOF is adjustable.Nineteen ninety-five, Westerlund etc. have prepared a kind of inwall and have connect amino quartz capillary column, possess the character that EOF is adjustable equally, and have been separated serial enkephalins with this pillar.1996, Colon etc. delivered similar work, and its gained coating is all highly stable under very low or very high pH value, and its Column preparation process is relatively simple, and has been separated adrenaline enantiomter, three kinds of alkaline proteins and four peptide species.
Recently, the concept of amino coating open tubular column is incorporated into the preparation process of capillary monolithic column by people, and amplification obtains mixed mode integral post further.2006, Ding Guosheng etc. with ethyl orthosilicate, aminopropyl triethoxysilane and octyltri-ethoxysilane for reacting common precursor, adopt sol-gel technique one-step method to prepare and there is anti-phase and mixed mode integral post that is weak anionic exchange interaction, be separated organic acid and neutral compound.The same year, Hu etc. have prepared mixed mode integral post by the one one-step hydrolysis-polymerization of TEOS, mercaptopropyltriethoxysilane and phenyl triethoxysilane, the sulfonic acid group on this integral post surface can produce stronger cathodic electricity seepage flow, and phenyl has anti-phase retention mechanism simultaneously.
But the report up to the present, about mixed mode open-tubular capillary chromatographic column Synthesis and applications is little.
Summary of the invention
The object of the present invention is to provide a kind of prepare simple, be easy to mixed mode open-tubular capillary chromatographic column of applying and preparation method thereof, and use it for capillary electric chromatogram compartment analysis.
Mixed mode open-tubular capillary chromatographic column provided by the invention, its principle obtains colloidal sol by the hydrolysis in variety classes silicon source, copolymerization, colloidal sol is poured in capillary with capillary tube inner wall bonding, one end, silicon source of functionalization is alkoxy grp, the silicone hydroxyl of the silica on itself and capillary tube inner wall reacts, the other end, with the functionalization such as octyl group, amino group, plays centrifugation.Specifically, mixed mode open-tubular capillary chromatographic column provided by the invention, the Stationary liquid on its chromatographic column inwall have simultaneously positively chargeable group, can be electronegative group and uncharged hydrophobic group three kinds of functional groups; The host material of open pipe chromatographic column can be quartz, glass, steel or organic polymer etc.
Wherein, described positively chargeable group can be that primary amine, secondary amine or tertiary amine etc. can accept proton and positively charged group.
Described can electronegative group, can be that hydroxyl, sulfydryl or sulfonic group etc. can lose proton and electronegative group.
Described hydrophobic group can be four carbon atom to the long-chain carbon of 18 carbon atoms or benzene ring type compounds.
The preparation method of mixed mode open-tubular capillary chromatographic column provided by the invention, is that silicon source, functionalized silicon source and ethanol are mixed with mixed solution by different proportion, then adds a small amount of water and hydrochloric acid, add thermal agitation under fixed temperature, obtained colloidal sol; This colloidal sol is coated in open tubular column inwall, obtained open pipe chromatographic column.Concrete steps are:
(1) preparation of colloidal sol: at 25-60
ounder C, the silicon source of 1 mL is dissolved in the ethanol of 0.5-2 mL, then adds the hydrochloric acid of 30 microlitre 2 mol/L, 25-80
oc adds thermal agitation 1-6 h, obtained colloidal sol; After question response liquid cool to room temperature, add 40-600 μ L functionalized silicon source (aminopropyl triethoxysilane and 20-300 μ L octyltri-ethoxysilane etc. as 20-300 μ L) wherein, through ultrasonic process 1-5 min, obtain last colloidal sol;
(2) preparation of open pipe electric chromatographic column: pour into above-mentioned colloidal sol in the capillary of cleaning treatment by certain pressure (as 2-5 atm), room temperature places 5 min-12 h; In 100-160
oat C temperature, logical nitrogen is rushed unreacted colloidal sol; Continue logical nitrogen 1-12 h at such a temperature again, make to react completely, namely obtain required mixed mode open-tubular capillary chromatographic column.
Get chromatogram column length 50 about cm during use and get final product (effective length 41 about cm).
In the present invention, the cleaning treatment step of capillary is: the quartz capillary newly the purchased NaOH of 1 mol/L is rinsed 1 h, with distilled water flushing 0.5 h, 1 h is rinsed again with the hydrochloric acid of 1 mol/L, finally use distilled water flushing 0.5 h, capillary is placed in gas-chromatography column oven, at 100-160
ological nitrogen drying 1-12 h under C.
In the present invention, described silicon source is methyl silicate (TMOS) or ethyl orthosilicate (TEOS).
In the present invention, described functionalized silicon source is octyltri-ethoxysilane (C8-TEOS), octyl group trimethoxy silane (C8-TMOS), octadecyltriethoxy silane (C18-TEOS), octadecyl trimethoxysilane (C18-TMOS), APTES (NH2-TEOS), 3-TSL 8330 (NH2-TMOS), 3-Mercaptopropyltriethoxysilane (SH-TEOS), 3-mercaptopropyi trimethoxy silane (SH-TMOS), phenyl propyl triethoxysilane (Ph-TEOS) or phenyl propyl trimethoxy silane (Ph-TMOS).
In the present invention, the size of the EOF of described open-tubular capillary chromatographic column, the separating property of chromatographic column can be regulated by the ratio in adjustment silicon source, functionalized silicon source.
In the present invention, can by the size and Orientation (Fig. 1) regulating the pH value of electrochromatography mobile phase used to regulate the EOF of described open-tubular capillary chromatographic column.
Gained open-tubular capillary chromatographic column of the present invention can be used in isolation technics, such as capillary electric chromatogram Separation of Neutral compound, acid compound and alkali compounds etc.Wherein, the separation of neutral compound is for polycyclic aromatic hydrocarbon (naphthalene, biphenyl, anthracene) and substituted benzene (toluene, ethylbenzene, propyl benzene, n-butyl benzene), and chromatogram is shown in Fig. 2 and Fig. 3; The separation of acid compound is with p-methyl benzenesulfonic acid, 4-aminobenzenesulfonic acid, salicylic acid, 3,5-dinitrobenzoic acids, phthalic acid, benzoic acid, p-aminobenzoic acid for example, and its chromatogram is shown in Fig. 4; The separation of alkali compounds is for meta nitro aniline, naphthalidine, ortho-aminotoluene, o-phenylenediamine, para-totuidine, and its chromatogram is shown in Fig. 5.
Accompanying drawing explanation
Fig. 1 is the EOF of open-tubular capillary chromatographic column of the present invention and the graph of a relation of pH.
Fig. 2 is that open-tubular capillary chromatographic column of the present invention is separated polycyclic arene compound chromatogram.
Fig. 3 is that open-tubular capillary chromatographic column of the present invention is separated substituted benzene chromatogram.
Fig. 4 is the chromatogram that open-tubular capillary chromatographic column of the present invention is separated acid compound.
Fig. 5 is the chromatogram that open-tubular capillary chromatographic column of the present invention is separated alkali compounds.
Detailed description of the invention
The preparation and characterization of embodiment 1 open pipe chromatographic column
Use the NaOH of 1 mol/L, distilled water, the hydrochloric acid of 1 mol/L, quartz capillary (54 cm are long) each 1 h of distilled water flushing 50 micron inside diameter successively, 120
othe dry capillary of logical nitrogen 1 h under C.
The preparation of colloidal sol: 1 mL TEOS and 30 μ L 2 mol/L HCl is added in 2 mL absolute ethyl alcohols, 60
oc adds thermal agitation 1 h, after cool to room temperature, adds the C8-TEOS of 96 μ L and the NH2-TEOS of 96 μ L, ultrasonic 1 min in above-mentioned solution, obtained colloidal sol.
In the quartz capillary processed above being poured into by pressure by this colloidal sol, room temperature places 10 min, and 120
ounder C, logical nitrogen is rushed unreacted colloidal sol, and 120
oc continues logical nitrogen 1 h to be made to react completely.
Adopt the CL1020 efficient capillary electrophoresis apparatus of Beijing Cai Lu scientific instrument Co., Ltd, under electrochromatography pattern, get the open pipe chromatographic column prepared above, with the cushioning liquid of different pH value for mobile phase, 20
oc ,+20 kV or-20 kV, under 210 nm conditions, are electroendosmotic flow marker with thiocarbamide, obtain the graph of a relation (Fig. 1) of EOF and pH.
EOF shows when being greater than zero that EOF flows to negative electrode from anode, shows that EOF overturns, flow to anode from negative electrode when being less than zero.Because amino and silicone hydroxyl are present in capillary tube inner wall simultaneously, the size and Orientation of EOF depends on the protonation of capillary tube inner wall amino group and the degree of ionization of silicone hydroxyl under given pH value.Residual hydroxy groups neutral when low ph value (< 5.7), on capillary tube inner wall, amino positively charged, cause mobile phase electronegative, therefore EOF is less than zero, flows to anode from negative electrode, so usual negative pole sample introduction.When high ph-values (> 5.7), the amino neutral on capillary tube inner wall, hydroxyl is electronegative, and cause mobile phase positively charged, EOF is greater than zero, flows to negative electrode from anode, so usual positive pole sample introduction.
The compartment analysis of embodiment 2 gained open tubular column centering compound
Adopt the CL1020 efficient capillary electrophoresis apparatus of Beijing Cai Lu scientific instrument Co., Ltd, under electrochromatography pattern, get the open pipe chromatographic column 41 cm(effective length prepared according to the embodiment of the present invention 1), Acetic acid-sodium acetate buffer system with 20 mM pH 2.6: methyl alcohol (80/20, v/v) be mobile phase, 20
oc ,-20 kV, under 210 nm conditions, thiocarbamide, naphthalene, biphenyl and anthracene realize being separated (Fig. 2), and wherein chromatographic peak is from left to right followed successively by: thiocarbamide, naphthalene, biphenyl, anthracene.Also can realize being separated (Fig. 3) at same experimental conditions Toluene, ethylbenzene, propyl benzene, n-butyl benzene, wherein chromatographic peak is from left to right followed successively by: toluene, ethylbenzene, propyl benzene, n-butyl benzene.
Embodiment 3 gained open tubular column is to the compartment analysis of acid compound
Adopt the CL1020 efficient capillary electrophoresis apparatus of Beijing Cai Lu scientific instrument Co., Ltd, under electrochromatography pattern, get the open pipe chromatographic column 41 cm(effective length prepared according to the invention process example 1), phosphoric acid buffer system with 20 mM pH 3.11: methyl alcohol (50/50, v/v) be mobile phase, 20
oc,-20 kV, under 210 nm conditions, can realize the separation (Fig. 4) to acid compound, in figure, chromatographic peak is from left to right followed successively by: p-methyl benzenesulfonic acid, sulfanilic acid, salicylic acid, 3,5-dinitrobenzoic acids, 4-nitrobenzoic acid, benzoic acid, p-aminobenzoic acid.
Embodiment 4 gained open tubular column is to the compartment analysis of alkali compounds
Adopt the CL1020 efficient capillary electrophoresis apparatus of Beijing Cai Lu scientific instrument Co., Ltd, under electrochromatography pattern, get the open pipe electric chromatographic column 41 cm(effective length prepared according to the invention process example 1), the HAc with 20 mM: methyl alcohol (70/30, v/v) be mobile phase, 20
oc ,-20 kV, under 210 nm conditions, can realize the separation (Fig. 5) to alkali compounds, in figure, chromatographic peak is from left to right followed successively by: meta nitro aniline, naphthalidine, ortho-aminotoluene, o-phenylenediamine, aniline, para-totuidine.
Claims (8)
1. a preparation method for mixed mode open-tubular capillary chromatographic column, is characterized in that concrete steps are:
(1) preparation of colloidal sol: at 25-60 DEG C, is dissolved in the silicon source of 1 mL in the ethanol of 0.5-2 mL, then adds the hydrochloric acid of 30 microlitre 2 mol/L, and 25-80 DEG C adds thermal agitation 1-6 h, obtained colloidal sol; After question response liquid cool to room temperature, add 40-600 μ L functionalized silicon source wherein, through ultrasonic process 1-5 min, obtain last colloidal sol;
(2) preparation of open pipe chromatographic column: above-mentioned colloidal sol is poured in the capillary of cleaning treatment by certain pressure, room temperature places 5 min-12 h; At 100-160 DEG C of temperature, logical nitrogen is rushed unreacted colloidal sol; Continue logical nitrogen 1-12 h at such a temperature again, make to react completely, namely obtain required mixed mode open-tubular capillary chromatographic column;
Wherein, described silicon source is methyl silicate or ethyl orthosilicate;
Described functionalized silicon source is octyltri-ethoxysilane, octyl group trimethoxy silane, octadecyltriethoxy silane, octadecyl trimethoxysilane, APTES, 3-TSL 8330,3-Mercaptopropyltriethoxysilane, 3-mercaptopropyi trimethoxy silane, phenyl propyl triethoxysilane, phenyl propyl trimethoxy silane.
2. preparation method according to claim 1, is characterized in that: regulate the size of the EOF of mixed mode open-tubular capillary chromatographic column, the separating property of chromatographic column by regulating silicon source, the consumption in functionalized silicon source and ratio; By the size and Orientation regulating the pH value of chromatogram mobile phase used to regulate the EOF of mixed mode open-tubular capillary chromatographic column.
3. the mixed mode open-tubular capillary chromatographic column obtained by preparation method described in claim 1, is characterized in that: the Stationary liquid on chromatographic column inwall have simultaneously positively chargeable group, can be electronegative group and uncharged hydrophobic group three kinds of functional groups.
4. mixed mode open-tubular capillary chromatographic column according to claim 3, is characterized in that: the host material of open pipe chromatographic column is quartz, glass, steel or organic polymer.
5. mixed mode open-tubular capillary chromatographic column according to claim 4, is characterized in that: the group that the group of described positively chargeable is primary amine, secondary amine or tertiary amine accept proton and positively charged.
6. mixed mode open-tubular capillary chromatographic column according to claim 5, is characterized in that: described can electronegative group be hydroxyl, sulfydryl or sulfonic group lose proton and electronegative group.
7. mixed mode open-tubular capillary chromatographic column according to claim 6, is characterized in that: described uncharged hydrophobic group is four carbon atom to the long-chain carbon of 18 carbon atoms or benzene ring type compounds.
8. the application of mixed mode open-tubular capillary chromatographic column in isolation technics as described in one of claim 3-7.
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| CN106198780A (en) * | 2016-06-24 | 2016-12-07 | 华南师范大学 | Protein modified open tubular column and the application in monoclonal antibody charge isomer separates |
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| CN110132668B (en) * | 2019-04-28 | 2022-02-15 | 西安培华学院 | Conventional glass slide super-hydrophobic treatment method |
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