CN101152624B - Alcoholic hydroxyl group hydrophily color spectrum stationary phase and method for preparing the same - Google Patents
Alcoholic hydroxyl group hydrophily color spectrum stationary phase and method for preparing the same Download PDFInfo
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- CN101152624B CN101152624B CN2006100479651A CN200610047965A CN101152624B CN 101152624 B CN101152624 B CN 101152624B CN 2006100479651 A CN2006100479651 A CN 2006100479651A CN 200610047965 A CN200610047965 A CN 200610047965A CN 101152624 B CN101152624 B CN 101152624B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
- B01D15/30—Partition chromatography
- B01D15/305—Hydrophilic interaction chromatography [HILIC]
Abstract
The invention provides an alcoholic hydroxyl group hydrophilic chromatographic fixed phase and the structure is right style, wherein, X is-OCH3 or-OCH2CH3, Y is-CH2OOC-or-CH2NHOC-; when m=0, n=0; when m=1, n=0-4. The invention adopts clickchemistry as bonding reaction method: firstly, azide group is lead in the surface of silica gel, and then water/alcohol or water/methyl alcohol mixing system isadopted as reaction solvent, monohydric or polyalcohol molecule decorated with terminal alkyne is bonded with the surface of silica gel, therefore, the alcoholic hydroxyl polar fixed phase is realized. The fixed phase has simple structure, stable nature (ionization cannot occur under the condition of acid-bases), simple preparation process (reaction occurs in water solution system at room temperature) and high efficiency (selectivity and transformation ratio of click chemistry is up to 100 percent). The polar fixed phase prepared with the method presents typical hydrophilic effect liquid phase chromatographic characteristics in water/acetonitrile (water content is less than 40 percent) flowing phase and has reservation and separated selection for polar compound.
Description
Technical field
The present invention relates to fixedly phase of liquid chromatogram, a kind of specifically alcoholic hydroxyl group hydrophily color spectrum is phase and preparation method thereof fixedly; It is to adopt click chemistry as the fixing phase of the alcoholic hydroxyl group hydrophily color spectrum of bonding reaction method.
Technical background
RPLC (RP-HPLC) is present the most widely used high efficient separation technology, but the hydrophobic fixedly phase of using in the reverse-phase chromatography (as C18, C8 etc.) to strong polar compound (as oligosaccharides, glucosides, strong polarity oligopeptides etc.) reservation is very weak, does not even keep.Reach the purpose of separation for strong polar compound there being stick effect preferably, using polar stationary phase is a kind of good approach.Hydrophilic interaction liquid chromatogram pattern (HILIC) is the chromatographic technique that is used to separate strong polar compound that development in recent years is got up, be similar to normal-phase chromatography, use the relative less mobile phase of polar stationary phase with polarity, but that different with normal-phase chromatography is moisture (water content is generally less than 40%) [Alpert during it flows mutually, A.J.J.Chromatogr.1990,499,177-196].Hydrophilic Interaction Chromatography is used to separate strong polar compound (as oligosaccharides, oligopeptides and polar medicine molecule etc.) existing bibliographical information [Strege, M.A.Anal.Chem.1998,70,2439-2445; Strege, M.A.et al, Anal.Chem.2000,72,4629-4633; Wang, X.D.et al, J.Chromatogr.A, 2005,1083,58-62; Tolstikov, V.V.et al, Anal.Biochem.2002,301,298-307; Yoshida, T.Anal.Chem.1997,69,3038-3043; Risley, D.S.et al, Anal.Chem.2000,72,1736-1739; Dallet, P.et al, J.Chromatogr.B 2000,742,447-452; Olsen, B.A.J.Chromatogr.A 2001,913,113-122].But the fixedly phase of hydrophilic Interaction Chromatography still is to use and is just fixing phase, mainly is directly to use silica gel, amino, and conduct such as cyano group is phase [Guo, Y.et al, J.Chromatogr.A, 2005,1074,71-80 fixedly; Garbis, S.D.et al, Anal.Chem.2001,73,5358-5364], exist short problem of poor reproducibility and service life.For example, the amino fixing meeting generation ionization under acid condition of bonding, changing its surface state with pH can change; Directly use silica gel then also can change surface texture because the silicon hydroxyl under alkali condition ionization takes place.The variation meeting of these surface textures causes uncertain influence to separation, particularly to very big influence is arranged in service life of reappearance and pillar.
At present, mutually at the early-stage for fixing of hydrophilic Interaction Chromatography exploitation specially, mainly be to contain formamido, the polymer bonds of hydroxyl is incorporated on the silica gel as hydrophilic fixedly phase, and commercial hydrophilic Interaction Chromatography is less [Guo, Y.et al of phase kind fixedly, J.Chromatogr.A, 2005,1074,71-80].At present, to the fixing comparative studies that lacks system mutually of all kinds of hydrophilic interactions, also be not widely used and generally accepted hydrophilic Interaction Chromatography fixing [Guo, Y.et al, J.Chromatogr.A, 2005,1074,71-80] mutually.
" click chemistry " (click chemistry) is the synthetic chemistry notion that the K.B.Sharpless professor (calendar year 2001 Nobel chemistry Prize winner) of U.S. Scripps research institute (ScrippsResearch Institute) proposed in calendar year 2001, its core content is: with high selectivity, high conversion, mild condition, chemical reaction simple to operate is realized the coupling of functional group, reaches the purpose of efficient production functional molecular and functional material.Current, the most widely used " click chemistry " (clickchemistry) reacts is Huisgen 1,3-diploar cycloaddition reaction, and its reaction equation is as follows:
" click chemistry " (click chemistry) has been applied in the research of surface of solids modification, but also do not use its fixedly report of phase bonding at present.
Summary of the invention
The object of the present invention is to provide fixedly phase and preparation method thereof of a kind of novel alcoholic hydroxyl group hydrophily color spectrum, to satisfy the separation that under hydrophilic interaction liquid chromatogram pattern, realizes strong polar compound.
For achieving the above object, the technical solution used in the present invention is:
A kind of alcoholic hydroxyl group hydrophily color spectrum is phase fixedly, and this bonding alcoholic extract hydroxyl group is fixing to be polar group with the alcoholic extract hydroxyl group, novel structure, and stable in properties, and contain the 1,2,3-triazoles ring structure in the structure, structure is
Wherein, X is-OCH
3Or-OCH
2CH
3, Y is-CH
2OOC-or-CH
2NHOC-; When m=0, n=0; When m=1, n=0～4.
The preparation of described fixedly phase uses click chemistry as bonding method, the bonding alcoholic extract hydroxyl group is as polar group, promptly utilize 1 of the alkynyl modified on the alcoholic hydroxy molecule in immobilized azido group on the silica gel and the solution, the 3-cycloaddition reaction realizes the bonding of alcoholic extract hydroxyl group.
At first introducing azido group on silica gel surface, is reaction dissolvent with water/ethanol or water/methyl alcohol mixed system then, with being modified with the monobasic of terminal alkyne or polyalcohol molecular linkage to the silica gel surface, promptly gets the alcoholic extract hydroxyl group polar stationary phase.Fixedly phase structure is simple for this, stable in properties (ionization does not take place under acid-base condition), preparation process simple (reacting in the water solution system under the room temperature), efficient (click chemistry selectivity and conversion ratio all can reach 100%).Adopt the polar stationary phase of this method preparation in water/acetonitrile (water content＜40%) flows mutually, to show typical hydrophilic interaction liquid chromatogram feature, polar compound is had good reservation and separation selectivity.
Concrete steps are as follows:
A. azido group is introduced on the silica gel surface: add silane coupler, sodium azide and catalyst in organic solvent, the mol ratio of silane coupler, sodium azide and catalyst is 1: (1.2-3): (0.01-0.1), under 60～130 ℃ of conditions, reacted 8～24 hours, add then through 6～18 hours micro-spherical silica gel of 160 ℃ of heating, the required silane coupler of every gram silica gel is 2-8mmol; Under 60～130 ℃ of conditions, continue reaction 12～24 hours, filter, use carrene successively with sand core funnel, ethanol, water, the acetone washing, gained solid in vacuum drying chamber under 40～80 ℃ of conditions dry 6～12 hours promptly gets (3-propyl group) azido silica gel;
The used silane coupler of step a has following structure:
Wherein, X is-OCH
3Or-OCH
2CH
3, A is Cl-or Br-.
This reaction is:
Wherein, X is-OCH
3Or-OCH
2CH
3, A is Cl-or Br-.Used organic solvent is acetonitrile, toluene or N, dinethylformamide, and the amount of the required organic solvent of every gram silica gel is 5-30mL; Catalyst is sodium iodide or KI; Spherical silica gel is the uniform full multi-hole blangel bead in particle diameter and aperture, and particle diameter is 5～40 μ m, and the aperture is 60～300A.
B.click chemistry bonding alcoholic extract hydroxyl group is phase fixedly: with adding volume ratio in (3-propyl group) azido silica gel of above-mentioned preparation is in 1/10～10/1 the water/methyl alcohol or water/alcohol mixed solvent, the required mixed solvent amount of every gram (3-propyl group) azido silica gel is 20-50mL, add the alcoholic extract hydroxyl group compound that is modified with terminal alkynyl again, catalyst, be modified with molar dose that the alcoholic extract hydroxyl group compound of terminal alkynyl adds and be 1～10 times of molar dose of nitrine on the silica gel, be preferably 2～5 times, catalyst is copper sulphate and sodium ascorbate, and used molar dose is respectively 1～10% and 2～40% of the alcoholic extract hydroxyl group compound molar dose that is modified with terminal alkynyl; Under 10～80 ℃ of conditions, reacted 24～72 hours, filter, use ethanol successively with sand core funnel, water, the weight concentration 2-20%EDTA aqueous solution, water, acetone washing, gained solid in vacuum drying chamber under 40～80 ℃ of conditions dry 6～12 hours, the i.e. fixing phase of alcoholic extract hydroxyl group;
The structure of the alcoholic extract hydroxyl group compound that is modified with terminal alkynyl that step b is used is:
Wherein Y is-CH
2OOC-or-CH
2NHOC-; When m=0, n=0; When m=1, n=0～4.
This reaction is:
Wherein, X is-OCH
3Or-OCH
2CH
3, Y is-CH
2OOC-or-CH
2NHOC-; During m=0, n=0; During m=1, n=0～4.Catalyst is copper sulphate and sodium ascorbate, and used dosage is respectively 1～10% and 2～40% (mol ratios) of the alcoholic extract hydroxyl group compound dosage that is modified with terminal alkynyl.
Description of drawings
Fig. 1 is the fixing chromatogram that is used for mutually under the hydrophilic pattern of the alcoholic extract hydroxyl group of the embodiment of the invention 1 preparation;
Fig. 2 is the fixing chromatogram that is applied to separate sugar mutually of the alcoholic extract hydroxyl group of the embodiment of the invention 1 preparation.
The present invention has following advantage:
1. adopt alcoholic extract hydroxyl group as the polar functionalities group, it is simple in structure, and can realize efficient separation to strong polar compound as polar stationary phase under hydrophilic interaction liquid chromatogram pattern;
2. alcoholic extract hydroxyl group is as functional group, and its character is very stable, and its surface texture can not change because of the change of pH, also is not easy to react with solute molecule, has avoided the amino fixedly unstability of phase structure of bonding commonly used.
3. adopt click chemistry as the bonding reaction method, can under the condition of gentleness, realize the immobilized of high selectivity and high conversion.
The specific embodiment
Fixedly phase of the present invention can be used under the hydrophilic Interaction Chromatography pattern separation to polar compound effectively.Below in conjunction with embodiment and accompanying drawing, the present invention will be further described.Embodiment only limits to illustrate the present invention, but not limitation of the invention.
In the 1000ml there-necked flask, add 500ml dry toluene, 45mmol (about 10ml) 3-chloropropyl triethoxysilane, 60mmol (about 4.0g) sodium azide, add 3.0mmol sodium iodide (about 0.5g) then as catalyst, 80 ℃ of following reaction 24h, adding particle diameter then is the spherical silica gel particle 20g of 5 μ m, reacts 24h again under 80 ℃, use carrene then successively, ethanol, water, each washed twice of acetone, each 200ml, the 60oC vacuum drying promptly got (3-propyl group) azido silica gel in 12 hours.(3-propyl group) azido silica gel adds 60ml water after getting the 2.5g drying in reactor, 60ml ethanol, 5mmol propilolic alcohol (about 0.3g), add 0.25mmol copper sulphate and 0.75mmol sodium ascorbate then as catalyst, react 48h under the room temperature, use ethanol, water successively, 10% the EDTA aqueous solution, water, each washed twice of acetone, each 100ml, vacuum drying promptly got product in 12 hours under the room temperature, and structure is:
Gained alcoholic extract hydroxyl group fixed phase stuffing is loaded in the stainless steel HPLC of 4.6mm*150mm chromatographic column, the chromatographic column that makes be used to test its under the hydrophilic chromatographic pattern to the reservation of strong polar compound with separate biased sample.The condition that is used to separate naphthalene and uracil is: acetonitrile/water is as flowing mutually, and the volume ratio of acetonitrile and water is 95 to 5, and flow velocity 0.6ml/min, column temperature are 30 ℃, and the detection wavelength is 254nm, and chromatogram is (1 is naphthalene, and 2 is uracil) shown in 1.Separating resulting shows, on alcoholic extract hydroxyl group post provided by the present invention, the strong polar compound uracil that the reverse-phase chromatographic column dead time flows out has obtained good reservation, and obtained good baseline separation with naphthalene, just in time opposite on both peak sequences and the conventional reversed-phase column, show typical hydrophilic interaction pattern feature and good separation selectivity.
Use embodiment 1 prepared chromatographic column to be separated in and separate monose and oligosaccharides under the hydrophilic Interaction Chromatography pattern.With acetonitrile/water as mobile phase, gradient elution (water volume content: 0-10 minute: 5-10%; 10-25 minute: 10%) under the condition, fructose, glucose, sucrose, maltose obtained good separation (as shown in Figure 2,1,2,3,4 are respectively fructose among the figure, glucose, sucrose, maltose).
Difference from Example 1 is, adopts the gluconic acid propynyl ester to replace propilolic alcohol, can get mutually fixing and this fixing chromatographic column of filling mutually of another kind of alcoholic extract hydroxyl group by the synthesis step of embodiment 1.Fixedly the structure of phase for its structure is:
In the 500ml there-necked flask, add 200ml dry toluene, 60mmol (about 15ml) 3-chloropropyl triethoxysilane, 60mmol (about 4.0g) sodium azide, add 5.0mmol sodium iodide (about 0.5g) then as catalyst, 110 ℃ of following reaction 24h, adding particle diameter then is the spherical silica gel particle 20g of 5 μ m, reacts 24h again under 110 ℃, use carrene then successively, ethanol, water, each washed twice of acetone, each 200ml, 60 ℃ of vacuum drying promptly got (3-propyl group) azido silica gel in 12 hours.(3-propyl group) azido silica gel adds 60ml water after getting the 2.5g drying in reactor, 60ml ethanol, 5mmol propilolic alcohol (about 0.3g), add 0.25mmol copper sulphate and 0.75mmol sodium ascorbate then as catalyst, react 48h under the room temperature, use ethanol, water successively, 10% the EDTA aqueous solution, water, each washed twice of acetone, each 100ml, vacuum drying promptly got product in 12 hours under the room temperature, and structure is:
In the 500ml there-necked flask, add 300ml anhydrous acetonitrile, 30mmol (about 7ml) 3-chloropropyl triethoxysilane, 40mmol (about 2.6g) sodium azide, add 3.0mmol sodium iodide (about 0.5g) then as catalyst, 80 ℃ of following reaction 24h, adding particle diameter then is the spherical silica gel particle 20g of 5 μ m, reacts 24h again under 80 ℃, use carrene then successively, ethanol, water, each washed twice of acetone, each 200ml, 60 ℃ of vacuum drying promptly got (3-propyl group) azido silica gel in 12 hours.(3-propyl group) azido silica gel adds 60ml water after getting the 2.5g drying in reactor, 60ml ethanol, 5mmol propilolic alcohol (about 0.3g), add 0.1mmol copper sulphate and 0.3mmol sodium ascorbate then as catalyst, react 48h under the room temperature, use ethanol, water successively, 10% the EDTA aqueous solution, water, each washed twice of acetone, each 100ml, vacuum drying promptly got product in 12 hours under the room temperature, and structure is:
In the 500ml there-necked flask, add the anhydrous N of 300ml, dinethylformamide, 30mmol (about 7ml) 3-chloropropyl triethoxysilane, 40mmol (about 2.6g) sodium azide, add 3.0mmol sodium iodide (about 0.5g) then as catalyst, 110 ℃ are reacted 24h down, adding particle diameter then is the spherical silica gel particle 20g of 5 μ m, react 24h under 110 ℃ again, use carrene, ethanol then successively, water, each washed twice of acetone, each 200ml, 60 ℃ of vacuum drying promptly got (3-propyl group) azido silica gel in 12 hours.(3-propyl group) azido silica gel adds 60ml water after getting the 2.5g drying in reactor, 60ml ethanol, 5mmol propilolic alcohol (about 0.3g), add 0.1mmol copper sulphate and 0.3mmol sodium ascorbate then as catalyst, react 48h under the room temperature, use ethanol, water successively, 10% the EDTA aqueous solution, water, each washed twice of acetone, each 100ml, vacuum drying promptly got product in 12 hours under the room temperature, and structure is:
Claims (7)
1. the fixing phase of an alcoholic hydroxyl group hydrophily color spectrum is characterized in that: its structure is,
Wherein, X is-OCH
3Or-OCH
2CH
3, Y is-CH
2OOC-or-CH
2NHOC-; When m=0, n=0; When m=1, n=0～4.
2. the preparation method of the described fixedly phase of claim 1 is characterized in that: use clickchemistry as bonding method, the bonding alcoholic extract hydroxyl group comprises the steps: as polar group
A. azido group is introduced on the silica gel surface: add silane coupler, sodium azide and catalyst in organic solvent, the mol ratio of silane coupler, sodium azide and catalyst is 1: 1.2-3: 0.01-0.1, under 60～130 ℃ of conditions, reacted 8～24 hours, add then through 6～18 hours micro-spherical silica gel of 160 ℃ of heating, the required silane coupler of every gram silica gel is 2-8mmol; Under 60～130 ℃ of conditions, continue reaction 12～24 hours, filter, use carrene successively with sand core funnel, ethanol, water, the acetone washing, gained solid in vacuum drying chamber under 40～80 ℃ of conditions dry 6～12 hours promptly gets (3-propyl group) azido silica gel;
B.click chemistry bonding alcoholic extract hydroxyl group is phase fixedly: with adding volume ratio in (3-propyl group) azido silica gel of above-mentioned preparation is in 1/10～10/1 the water/methyl alcohol or water/alcohol mixed solvent, the required mixed solvent amount of every gram (3-propyl group) azido silica gel is 20-50mL, add the alcoholic extract hydroxyl group compound that is modified with terminal alkynyl again, catalyst, be modified with molar dose that the alcoholic extract hydroxyl group compound of terminal alkynyl adds and be 1～10 times of molar dose of nitrine on the silica gel, catalyst is copper sulphate and sodium ascorbate, and used molar dose is respectively 1～10% and 2～40% of the alcoholic extract hydroxyl group compound molar dose that is modified with terminal alkynyl; Under 10～80 ℃ of conditions, reacted 24～72 hours, filter, use ethanol successively with sand core funnel, water, the weight concentration 2-20%EDTA aqueous solution, water, acetone washing, gained solid in vacuum drying chamber under 40～80 ℃ of conditions dry 6～12 hours, the i.e. fixing phase of alcoholic extract hydroxyl group.
3. according to the described preparation method of claim 2, it is characterized in that: the used organic solvent of step a is an acetonitrile, toluene or N, dinethylformamide; The amount of the required organic solvent of every gram silica gel is 5-30mL.
4. according to the described preparation method of claim 2, it is characterized in that: the used silane coupler of step a has following structure:
Wherein, X is-OCH
3Or-OCH
2CH
3, A is Cl-or Br-.
5. according to the described preparation method of claim 2, it is characterized in that: the used catalyst of step a is sodium iodide or KI.
6. according to the described preparation method of claim 2, it is characterized in that: the structure of the alcoholic extract hydroxyl group compound that is modified with terminal alkynyl that step b is used is:
Wherein Y is-CH
2OOC-or-CH
2NHOC-; When m=0, n=0; When m=1, n=0～4.
7. according to the described preparation method of claim 2, it is characterized in that: the mol ratio dosage of the alcoholic extract hydroxyl group compound that is modified with terminal alkynyl that step b is used is 2～5 times of mol ratio dosage of nitrine on the silica gel.
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| US20020058588A1 (en) * | 2000-06-23 | 2002-05-16 | National University Of Singapore | Materials comprising saccharide cross-linked and chemically bonded to a support via urea linkages useful for chromatography and electrophoresis applications |
| CN1595143A (en) * | 2004-06-29 | 2005-03-16 | 武汉大学 | Highlyerformance liquid phase chromatogram fixed phase, method for making same and use thereof |
| CN1624473A (en) * | 2003-12-05 | 2005-06-08 | 中国科学院大连化学物理研究所 | Method of fust preparing linkage type polysaccharide chiral fixed phase |
| CN1624472A (en) * | 2003-12-05 | 2005-06-08 | 中国科学院大连化学物理研究所 | Preparing linkage type polysaccharide chiral fixed phase by free radical copoly merization method |
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| US20020058588A1 (en) * | 2000-06-23 | 2002-05-16 | National University Of Singapore | Materials comprising saccharide cross-linked and chemically bonded to a support via urea linkages useful for chromatography and electrophoresis applications |
| CN1624473A (en) * | 2003-12-05 | 2005-06-08 | 中国科学院大连化学物理研究所 | Method of fust preparing linkage type polysaccharide chiral fixed phase |
| CN1624472A (en) * | 2003-12-05 | 2005-06-08 | 中国科学院大连化学物理研究所 | Preparing linkage type polysaccharide chiral fixed phase by free radical copoly merization method |
| CN1595143A (en) * | 2004-06-29 | 2005-03-16 | 武汉大学 | Highlyerformance liquid phase chromatogram fixed phase, method for making same and use thereof |
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Denomination of invention: An alcohol hydroxyl hydrophilic chromatographic stationary phase and its preparation method Effective date of registration: 20210625 Granted publication date: 20100929 Pledgee: Zhejiang Wenling Rural Commercial Bank Co.,Ltd. Pledgor: Zhejiang Huapu Xinchuang Technology Co.,Ltd. Registration number: Y2021330000676 |
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| PE01 | Entry into force of the registration of the contract for pledge of patent right |