CN101757897A - Chitosan oligosaccharide hydrophilic interaction chromatography stationary phase and preparation method thereof - Google Patents
Chitosan oligosaccharide hydrophilic interaction chromatography stationary phase and preparation method thereof Download PDFInfo
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- CN101757897A CN101757897A CN200910197312A CN200910197312A CN101757897A CN 101757897 A CN101757897 A CN 101757897A CN 200910197312 A CN200910197312 A CN 200910197312A CN 200910197312 A CN200910197312 A CN 200910197312A CN 101757897 A CN101757897 A CN 101757897A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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]
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Abstract
The invention relates to a preparation method for a chitosan oligosaccharide hydrophilic interaction chromatography stationary phase. The click chemistry is adopted as a bonding reaction method for bonding chitosan oligosaccharide, firstly, terminal alkynyl is introduced on the surface of silica gel, secondly, the following solvents of water and methanol or the mixture of the solvents is taken as the reaction solvent, and then the chitosan oligosaccharide modified with azido group is bonded to the surface of the silica gel to obtain the chitosan oligosaccharide hydrophilic interaction chromatography stationary phase; the chitosan oligosaccharide is adopted as the polarity functional group with simple structure, and the chitosan oligosaccharide taken as the polarity stationary phase can realize the highly effective separation to the strongly polar compounds under the hydrophilic interaction liquid chromatogram mode; the chitosan oligosaccharide taken as the functional group has stable property, the surface structure does not change due to the change of pH, and the chitosan oligosaccharide is not liable to react with the solute molecule; and the click chemistry is adopted as the bonding reaction method, therefore, the purpose of immobilization with high selectivity and high transformation ratio can be achieved under the mild conditions.
Description
[technical field]
The present invention relates to fixedly phase technology of liquid chromatogram, specifically, is a kind of use " link chemistry " (click chemistry) as the fixing preparation method of phase of bonding method bonding chitosan oligosaccharide hydrophilic interaction chromatography.
[technical background]
Hydrophilic Interaction Chromatography (the English HILIC that is called for short) is the chromatographic technique that is used to separate strong polar compound that development in recent years is got up, be a kind of with polar stationary phase (as the silica gel or the silica gel of deriving) and contain high concentration polar organic solvent and low concentration aqueous solution chromatogram mode for flowing mutually, it has solved fixedly phase of conventional inverter chromatogram hydrophobicity, as C18, C8 etc. are to strong polar compound, as oligosaccharides, and glucosides, strong polarity oligopeptides etc. keep very weak, even uncensored problem.Hydrophilic Interaction Chromatography is used for the separating polar compound, as amino acid, and existing bibliographical informations such as peptide and sugar.The fixedly phase of hydrophilic Interaction Chromatography still is to use and is just fixing phase, mainly be directly to use fixedly phase of conducts such as silica gel, amino, amide groups, glycol-based, carbohydrate, but, dissimilar fixing different retention mechanisms and the separation efficiencies of existing mutually, certainly, fixing some bigger shortcomings that exist mutually of some type, for example, the Irreversible Adsorption phenomenon takes place in silicagel column easily, and nh 2 column meeting and carbohydrate generate Schiff alkali, thereby influence separates.At present, mutually at the early-stage for fixing of hydrophilic Interaction Chromatography exploitation specially, fixedly the phase kind is less for commercial hydrophilic Interaction Chromatography, thereby needs the fixing demand for development that satisfies hydrophilic Interaction Chromatography mutually of exploitation other types.
" link chemistry " or wait proposition by Bei Rui Sharp sharp this (K.Barry Sharpless) for " click chemistry " (click chemistry), its core is to obtain molecular diversity widely with a small amount of simple and reliable and chemical transformation high selectivity, it has started fast, effectively or even 100% reliably, highly selective makes the synthetic chemistry frontier of all kinds of noval chemical compounds.Wherein, the reaction of extensive use is Huisgen 1 the most, 3-diploar cycloaddition reaction, and it has brought into play very important effect in synthesizing of chromatographic stationary phase, and its reaction equation is as follows:
[summary of the invention]
The object of the present invention is to provide fixedly phase and preparation method thereof of a kind of novel chitosan oligosaccharide hydrophilic interaction chromatography, to satisfy the separation that under the hydrophilic Interaction Chromatography pattern, realizes strong polar compound.
For achieving the above object, the technical solution used in the present invention is:
A kind of chitosan oligosaccharide hydrophilic interaction chromatography is phase fixedly, and its structure is:
Wherein, n=1～9,
The 1,2,3-triazoles ring position is uncertain.
A kind of chitosan oligosaccharide hydrophilic interaction chromatography is the preparation method of phase fixedly, it is characterized in that, uses " link chemistry " as bonding method bonding chitosan oligosaccharide molecule, to may further comprise the steps:
(1) alkynyl is introduced on the silica gel surface
1. add silane coupler, propargylamine in organic solvent, the mol ratio of silane coupler, propargylamine is 1～5: 1.2～5, reacts 6～36 hours under 60～150 ℃ of conditions;
2. add the micro-spherical silica gel of activation then, the required silane coupler of every gram micro-spherical silica gel is 1～10mmol;
3. continuing reaction under 80～120 ℃ of conditions after 12～48 hours, filter, with carrene, methyl alcohol, acetone washing, obtain solids successively with sand core funnel;
4. with the 3. solids of gained in vacuum drying chamber under 40～120 ℃ of conditions dry 6～12 hours of step (1), promptly get terminal alkynyl silica gel;
(2) use fixedly phase of " link chemistry " bonding chitosan oligosaccharide
1. the alkynyl silica gel of step (1) preparation is added volume ratio and be in water/methyl alcohol mixed solvent of 2/1～10/1, the required mixed solvent amount of every gram alkynyl silica gel 20～50mL;
2. add chitosan oligosaccharide and the catalyst that is modified with azido group again, be modified with molar dose that the chitosan oligosaccharide of azido group adds and be 1～15 times of molar dose of alkynyl on the silica gel, catalyst is cupric and sodium ascorbate, used molar dose be respectively alkynyl on the silica gel molar dose 1～10% and 2～40%;
3. after reacting 72～200 hours under 10～80 ℃ of conditions, filter with sand core funnel, water, weight concentration are 2～20% EDTA two sodium water solutions, water, methyl alcohol, acetone washing successively, obtain solids;
4. with the 3. solids of gained in vacuum drying chamber under 40～80 ℃ of conditions dry 6～12 hours of step (2), promptly get fixedly phase of chitosan oligosaccharide hydrophilic interaction chromatography.
The organic solvent that above-mentioned steps (1) 1. adopts is N, the N--dimethyl formamide, and the amount of the required organic solvent of every gram silica gel is 5～30mL.
The structure of the silane coupler that above-mentioned steps (1) 1. adopts is:
Its reaction equation is:
The micro-spherical silica gel that above-mentioned steps (1) 2. adopts is to be the uniform full multi-hole blangel orbicule of particle diameter and aperture, and its particle diameter is 5～40 μ m, and the aperture is 60～300
The structure of the chitosan oligosaccharide that is modified with azido group that above-mentioned steps (2) 2. adopts is:
Wherein, n=1～9,
The azido position is uncertain,
The reaction equation of step (2) is:
Wherein, the structure of R is:
In the formula, n=1～9,
The azido position is uncertain;
The molar dose of the chitosan oligosaccharide that is modified with azido group that above-mentioned steps (2) 2. adopts is 1～5 times of molar dose of alkynyl on the silica gel.
The catalyst that above-mentioned steps (2) 2. adopts is cupric and sodium ascorbate, and used dosage is respectively 5～10% and 10～30% of the silica gel molar dose that is modified with terminal alkynyl.
Good effect of the present invention is:
(1) adopt chitosan oligosaccharide 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) chitosan oligosaccharide 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.
(3) adopt " link chemistry ", can under the condition of gentleness, realize the immobilized of high selectivity and high conversion as the bonding reaction method.
[description of drawings]
Accompanying drawing 1 is the fixing preparation method's of phase the FB(flow block) of chitosan oligosaccharide hydrophilic interaction chromatography of the present invention;
Accompanying drawing 3 is the fixing chromatogram that is used for separating under the hydrophilic pattern oligosaccharides mutually of the chitosan oligosaccharide of embodiment of the invention preparation;
[specific embodiment]
Chitosan oligosaccharide hydrophilic interaction chromatography of the present invention is fixing can be used under the hydrophilic Interaction Chromatography pattern separation of polar compound is provided embodiments of the invention below in conjunction with description of drawings mutually effectively, and the present invention is described further; The embodiment that provides only limits to illustrate the present invention, but not to the qualification of the scope of the present invention.
Embodiment comprises following steps:
(1) preparation of nitrine sulphonyl imidazole hydrochloride
(about 4mL) is added dropwise to 50mmol NaN under ice-water bath with the 50mmol sulfonic acid chloride
3In the suspension of the anhydrous MeCN of 100mL of (about 3.2g), mixture at room temperature stirs and spends the night;
(about 6.8g) slowly adds in the above-mentioned system under ice-water bath with the 100mmol imidazoles, and the emulsion that obtains at room temperature stirs again and spends the night;
In mixture, add the dilution of 75mL ethyl acetate, use 2 * 75mL H successively
2O, the saturated NaHCO of 2 * 120mL
3Solution extracts, and organic facies adds anhydrous Na
2SO
4Drying, suction filtration, salify: the EtOH solution (the 5.4mL chloroacetic chloride is added drop-wise among the 19mLEtOH under ice-water bath and generates) of HCl is added drop-wise in the above-mentioned organic facies, separates out white solid, suction filtration with the ethyl acetate washing, obtains solid nitrine sulphonyl imidazole hydrochloride;
(2) preparation of nitrine chitosan oligosaccharide
1.2mmol nitrine sulphonyl imidazole hydrochloride (about 0.25g) is added by 0.66g chitosan oligosaccharide, 2mmolK
2CO
3(0.28g), 10 μ mol CuSO
45H
2In the mixture that O (2.5mg) and 5mL MeOH constitute, at room temperature react 17 hours (h), concentrate, remove MeOH, add a small amount of EtOH, ultrasonic, suction filtration, with the EtOH washing, the filbert solid that obtains is the nitrine chitosan oligosaccharide;
(3) preparation of alkynyl silica gel
In the 250mL there-necked flask, add the anhydrous N of 100mL, dinethylformamide, 35mmol (about 8.66mL) 3-isocyanic acid propyl-triethoxysilicane, 42mmol propargylamine (about 2.88mL), 12 hours (h) of reaction under 85 ℃ of conditions, adding particle diameter then is the spherical silica gel particle 10g of 5 μ m, under 110 ℃ of conditions, react again 31 hours (h), then successively with 300mL carrene, 500mL methyl alcohol, the washing of 250mL acetone, vacuum drying is 7 hours under 60 ℃ of conditions, promptly obtains terminal alkynyl silica gel;
(4) utilize fixedly phase of " link chemistry " preparation chitosan oligosaccharide hydrophilic interaction chromatography
Get the dried terminal alkynyl silica gel of 2.5g and place reactor, add 60mL water, 30mL methyl alcohol, 5mmol nitrine chitosan oligosaccharide (about 2.10g), add 0.25mmol copper sulphate and 0.75mmol sodium ascorbate then as catalyst, 108 hours (h) of reaction under the room temperature, EDTA two sodium solutions, 300mL water, 250mL acetone with 500mL water, 300mL 10% washs successively, vacuum drying is 12 hours under the room temperature, promptly gets fixedly phase product of chitosan oligosaccharide, and its structure is:
(n=1～9, the 1,2,3-triazoles ring position is uncertain);
(5) the dress post carries out chromatographic evaluation
Load mutually in the stainless steel HPLC of 2.1mm * 100mm chromatographic column the chitosan oligosaccharide hydrophilic interaction chromatography of gained is fixing, 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 nucleosides is: acetonitrile/water is as the phase that flows, the volume ratio of acetonitrile and water is 90: 10, flow velocity 0.2mL/min, column temperature are 30 ℃, and the detection wavelength is 254nm, (1 is uracil to chromatogram among the figure as shown in Figure 2,2 is uridine, and 3 is adenine, and 4 is cytimidine, 5 is cytidine, and 6 is guanosine); Separating resulting shows, on chitosan oligosaccharide 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 other nucleosides have obtained good baseline separation, shows typical hydrophilic interaction pattern feature and good separation selectivity.
The condition that is used to separate oligosaccharides is: acetonitrile/100mM Ammoniom-Acetate/water is as the phase that flows, gradient elution, 0min, acetonitrile (85), 100mM ammonium acetate (10), water (5); 20min, acetonitrile (75), 100mM ammonium acetate (10), water (15), flow velocity 0.2mL/min, column temperature are 30 ℃, evaporative light-scattering detects: nitrogen atomization atmospheric pressure: 25psi; Drift tube temperature: 70 ℃, gain: 100, chromatogram is (1 is wood sugar among the figure, and 2 is glucose, and 3 is turanose, and 4 is trehalose, and 5 is melezitose, and 6 is raffinose) as shown in Figure 3; Separating resulting shows that on chitosan oligosaccharide post provided by the present invention, several monose and oligosaccharides have obtained good baseline separation, show typical hydrophilic interaction pattern feature and good separation selectivity.
Claims (9)
1. the fixing phase of a chitosan oligosaccharide hydrophilic interaction chromatography is characterized in that its structure is:
Wherein, n=1～9,
The 1,2,3-triazoles ring position is uncertain.
2. the fixing preparation method of phase of a chitosan oligosaccharide hydrophilic interaction chromatography as claimed in claim 1 is characterized in that, uses " link chemistry " as bonding method bonding chitosan oligosaccharide molecule, to may further comprise the steps:
(1) alkynyl is introduced on the silica gel surface
1. add silane coupler, propargylamine in organic solvent, the mol ratio of silane coupler, propargylamine is 1～5: 1.2～5, reacts 6～36 hours under 60～150 ℃ of conditions;
2. add the micro-spherical silica gel of activation then, the required silane coupler of every gram micro-spherical silica gel is 1～10mmol;
3. continuing reaction under 80～120 ℃ of conditions after 12～48 hours, filter, with carrene, methyl alcohol, acetone washing, obtain solids successively with sand core funnel;
4. with the 3. solids of gained in vacuum drying chamber under 40～120 ℃ of conditions dry 6～12 hours of step (1), promptly get terminal alkynyl silica gel;
(2) use fixedly phase of " link chemistry " bonding chitosan oligosaccharide
1. the alkynyl silica gel of step (1) preparation is added volume ratio and be in water/methyl alcohol mixed solvent of 2/1～10/1, the required mixed solvent amount of every gram alkynyl silica gel 20～50mL;
2. add chitosan oligosaccharide and the catalyst that is modified with azido group again, be modified with molar dose that the chitosan oligosaccharide of azido group adds and be 1～15 times of molar dose of alkynyl on the silica gel, catalyst is cupric and sodium ascorbate, used molar dose be respectively alkynyl on the silica gel molar dose 1～10% and 2～40%;
3. after reacting 72～200 hours under 10～80 ℃ of conditions, filter with sand core funnel, water, weight concentration are 2～20% EDTA two sodium water solutions, water, methyl alcohol, acetone washing successively, obtain solids;
4. with the 3. solids of gained in vacuum drying chamber under 40～80 ℃ of conditions dry 6～12 hours of step (2), promptly get fixedly phase of chitosan oligosaccharide hydrophilic interaction chromatography.
3. chitosan oligosaccharide hydrophilic interaction chromatography according to claim 2 is the preparation method of phase fixedly, it is characterized in that, the organic solvent that above-mentioned steps (1) 1. adopts is N, the N--dimethyl formamide, and the amount of the required organic solvent of every gram silica gel is 5～30mL.
4. chitosan oligosaccharide hydrophilic interaction chromatography according to claim 2 is the preparation method of phase fixedly, it is characterized in that, the structure of the silane coupler that above-mentioned steps (1) 1. adopts is:
Its reaction equation is:
5. chitosan oligosaccharide hydrophilic interaction chromatography according to claim 2 is the preparation method of phase fixedly, it is characterized in that, the micro-spherical silica gel that above-mentioned steps (1) 2. adopts is to be the uniform full multi-hole blangel orbicule of particle diameter and aperture, and its particle diameter is 5～40 μ m, and the aperture is
6. chitosan oligosaccharide hydrophilic interaction chromatography according to claim 2 is the preparation method of phase fixedly, it is characterized in that, the structure of the chitosan oligosaccharide that is modified with azido group that above-mentioned steps (2) 2. adopts is:
Wherein, n=1～9,
The azido position is uncertain.
7. chitosan oligosaccharide hydrophilic interaction chromatography according to claim 2 is the preparation method of phase fixedly, it is characterized in that, the reaction equation of step (2) is:
Wherein, the structure of R is:
In the formula, n=1～9,
The azido position is uncertain.
8. chitosan oligosaccharide hydrophilic interaction chromatography according to claim 2 is the preparation method of phase fixedly, it is characterized in that, the molar dose of the chitosan oligosaccharide that is modified with azido group that above-mentioned steps (2) 2. adopts is 1～5 times of molar dose of alkynyl on the silica gel.
9. chitosan oligosaccharide hydrophilic interaction chromatography according to claim 2 is the preparation method of phase fixedly, it is characterized in that, the catalyst that above-mentioned steps (2) 2. adopts is cupric and sodium ascorbate, used dosage be respectively alkynyl on the silica gel molar dose 5～10% and 10～30%.
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Cited By (9)
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| CN102614847A (en) * | 2011-01-28 | 2012-08-01 | 中国科学院大连化学物理研究所 | Amphoteric ion hydrophilic chromatographic stationary phase and preparation method thereof |
| CN103638913A (en) * | 2013-11-27 | 2014-03-19 | 华东理工大学 | Bonding polysaccharide type hydrophilic chromatographic stationary phase as well as preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102614847B (en) * | 2011-01-28 | 2013-12-18 | 浙江华谱新创科技有限公司 | Amphoteric ion hydrophilic chromatographic stationary phase and preparation method thereof |
| CN102614847A (en) * | 2011-01-28 | 2012-08-01 | 中国科学院大连化学物理研究所 | Amphoteric ion hydrophilic chromatographic stationary phase and preparation method thereof |
| CN103638913A (en) * | 2013-11-27 | 2014-03-19 | 华东理工大学 | Bonding polysaccharide type hydrophilic chromatographic stationary phase as well as preparation method and application thereof |
| CN104148037A (en) * | 2014-08-08 | 2014-11-19 | 华东理工大学 | Arginine bonded type hydrophilic chromatography stationary phase and preparation method thereof |
| CN104324707A (en) * | 2014-09-16 | 2015-02-04 | 华东理工大学 | Amino diacid hydrophilic chromatographic stationary phase and preparation method thereof |
| CN104826618B (en) * | 2015-04-20 | 2017-05-24 | 华东理工大学 | Aminodiol hydrophilic chromatography stationary phase and preparation method thereof |
| CN104826618A (en) * | 2015-04-20 | 2015-08-12 | 华东理工大学 | Aminodiol hydrophilic chromatography stationary phase and preparation method thereof |
| CN105214616A (en) * | 2015-11-17 | 2016-01-06 | 华东理工大学 | The preparation method of acid sugar compounds application type hydrophilic chromatographic stationary phase and application |
| CN107556479A (en) * | 2017-10-19 | 2018-01-09 | 苏州大学 | A kind of hyperbranched polyorganosiloxane and preparation method thereof |
| CN107722266A (en) * | 2017-10-19 | 2018-02-23 | 苏州大学 | A kind of hyperbranched polyorganosiloxane/cyanate ester resin and preparation method thereof |
| CN107722266B (en) * | 2017-10-19 | 2020-06-16 | 苏州大学 | Hyperbranched polysiloxane/cyanate ester resin and preparation method thereof |
| CN107556479B (en) * | 2017-10-19 | 2020-07-21 | 苏州大学 | Hyperbranched polysiloxane and preparation method thereof |
| CN109232918A (en) * | 2018-09-04 | 2019-01-18 | 洛阳师范学院 | Supermolecule coordination polymer metal gel and preparation method thereof based on oxybisacetic acid and azide anion |
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Application publication date: 20100630 |