CN109926034B - Preparation and application of silica gel chromatographic packing modified by amphiphilic ionic liquid - Google Patents
Preparation and application of silica gel chromatographic packing modified by amphiphilic ionic liquid Download PDFInfo
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Abstract
The invention provides a preparation method of a silica gel chromatographic packing modified by amphiphilic ionic liquid, which is obtained by preparing norbornene methylene imidazole hexafluorophosphate ionic liquid on the surface of a silicon dioxide microsphere through ROMP technology and ATRP technology. The conjugated ring structure of imidazolium makes the surface of the fixed phase possess great pi electron system, so that it has relatively high separation performance on polycyclic aromatic hydrocarbon compound and benzene homolog. Meanwhile, due to the synergy of the ionic liquid chromatographic filler and the hydrophilic monomer poly (ethylene glycol) methacrylate, the ionic liquid chromatographic filler has a good separation effect on hydrophilic compounds such as amino acid and saccharides, and particularly has an outstanding separation effect on 10 kinds of small molecular saccharides such as D-ribose, xylose, DL-arabinose, D-fructose, glucose, sucrose, maltose, lactose, D-melezitose and raffinose.
Description
Technical Field
The invention relates to a chromatographic packing for detecting micromolecular sugar, in particular to a silica gel chromatographic packing modified by amphiphilic ionic liquid and a preparation method thereof, belonging to the technical field of high performance liquid chromatography detection.
Background
The ionic liquid has the advantages of non-volatility, non-flammability, strong conductivity, large viscosity (at room temperature), large heat capacity, small vapor pressure, stable property and good solubility to a plurality of inorganic salts and organic matters, and the ionic liquid is widely applied to the fields of electrochemistry, organic synthesis, catalysis, separation and the like because of the physicochemical properties. The preparation of high performance liquid chromatography materials by ionic liquids is one of the hot spots in current chromatographic material research, and in the chromatographic separation, the ionic liquids are used as mobile phase additives or modified on the surface of silica gel, but due to the difference of cations and anions forming the ionic liquids, the ionic liquids containing different cations and anions have certain difference of hydrophilicity and hydrophobicity.
Disclosure of Invention
The invention aims to provide a preparation method of silica gel chromatographic packing modified by amphiphilic ionic liquid aiming at the problem that the ionic liquid has hydrophilic-hydrophobic property difference in the current chromatographic separation;
the invention also aims to analyze and research the separation effect of the prepared amphiphilic ionic liquid modified silica gel chromatographic packing on various small molecular sugars.
Preparation of amphiphilic ionic liquid modified silica gel chromatographic packing
(1) Activation of silica gel: and acidifying porous spherical silica gel for chromatography by concentrated hydrochloric acid, washing to be neutral, washing by methanol, and drying in vacuum (drying at 50-70 ℃ for 6-8 h) to obtain activated silica gel. The concentration of the hydrochloric acid is 10-12 mol/L, and the soaking treatment time is 45-48 h.
(2) Preparation of aminopropyl silica gel: adding activated silica gel into anhydrous toluene, adding aminopropyl trimethoxysilane, and stirring and refluxing for 45-48 hours at 120-130 ℃; and (3) centrifugally washing the product with toluene, ethanol and methanol respectively, and drying in vacuum to obtain the aminopropyl silica gel. The mass ratio of the silica gel to the aminopropyltrimethoxysilane is 1: 1-1: 1.1.
(3) Preparation of amide silica gel: under the protection of nitrogen, sodium borate tetradecahydrate is used as a catalyst, and in a weak alkaline solution (with the pH of 9-10), aminopropyl silica gel and 2-bromoisobutyryl bromide are stirred and refluxed for 10-12 hours at the temperature of 20-25 ℃; washing the product with ethyl acetate and saturated salt solution in sequence, and drying in vacuum to obtain the amide silica gel. The mass-volume ratio of the aminopropyl silica gel to the 2-bromoisobutyryl bromide is 3.5: 1-3.6: 1 (g/mL).
(4) Preparation of polymerized ionic liquid modified silica gel: in dichloromethane, under the protection of argon and the action of a Grubbs catalyst, carrying out ring-opening metathesis polymerization on the silica gel containing acyl bromide groups and norbornene methylene imidazole hexafluorophosphate ionic liquid at the temperature of 20-25 ℃ for 1.8-2 h, washing with dichloromethane to remove the excessive Grubbs catalyst, and drying to obtain the silica gel modified by the polymerized ionic liquid.
The mass ratio of the acyl bromide group-containing silica gel to the norbornene methylene imidazole hexafluorophosphate ionic liquid is 1: 0.12-1: 0.14; the using amount of the Grubbs catalyst is 3-4% of the mass of the silica gel containing the acyl bromide groups.
(5) Preparation of target chromatographic packing: sequentially adding cuprous bromide and 2, 2-bipyridyl into a methanol-water mixed solution of hydrophilic monomer poly (ethylene glycol) methacrylate (the volume ratio of methanol to water is 1: 3.5-1: 4) under the protection of nitrogen, stirring and mixing uniformly, adding polymeric ionic liquid modified silica gel, mixing, carrying out ATRP reaction for 3.5-4 h at normal temperature, washing, and drying to obtain the target chromatographic filler.
The addition amount of the cuprous bromide catalyst is 0.6-0.7% of the mass ratio of the hydrophilic monomer poly (ethylene glycol) methacrylate. The 2, 2-bipyridyl has the effect of improving the activity of the catalyst, and the addition amount of the 2, 2-bipyridyl is 2-3% of the mass ratio of the hydrophilic monomer methacrylic acid poly (ethylene glycol) ester.
FIG. 1 is a schematic diagram of the synthesis of the amphiphilic ionic liquid modified silica gel chromatographic packing of the invention. FIG. 2 is an infrared characterization diagram of the amphiphilic ionic liquid modified silica gel chromatographic packing of the invention. Wherein 2982cm-1Stretching vibration of 800cm in methylene CH-1And 1460cm-1Deformation vibration of CH 1660cm-1The weak absorption of the band is C = C, and 948cm-1Out-of-plane rocking vibration at olefinic bond, 3409cm-1Stretching of CH at imidazole ring, 1734cm-1Vibration of the skeleton at imidazole ring, and 1534cm-1Where represents the amide II band and 1216cm-1And (b) represents an amide III band. As can be seen from fig. 1 and 2, the invention prepares the norbornene methylene imidazole hexafluorophosphate ionic liquid on the surface of the silica microsphere by the Ring Opening Metathesis Polymerization (ROMP) technology and the Atom Transfer Radical Polymerization (ATRP) technology. The conjugated ring structure of imidazolium makes the fixed phase surface possess large pi electron system, so that it has strong separation performance to polycyclic aromatic hydrocarbon compound and benzene homologThe larger the conjugated ring, the longer the retention time, and the addition of methanol in the mobile phase can weaken the retention of the polycyclic aromatic hydrocarbon compound. Meanwhile, due to the synergy of the ionic liquid chromatographic packing and hydrophilic monomer poly (ethylene glycol) methacrylate, the ionic liquid chromatographic packing has good separation effect on hydrophilic compounds such as amino acid and saccharides. The silica gel chromatographic packing modified by the amphiphilic ionic liquid prepared by the invention has the excellent physical structure of a silica gel matrix and the special chromatographic performance of the ionic liquid, and can separate hydrophobic analytes, ionic analytes and hydrophilic analytes.
Application of chromatographic separation material in detection of small molecular sugar
The liquid chromatography separation method comprises the following steps: mobile phase: acetonitrile-water; 20 μ L of injection (150X 4.6mm I.D.).
Elution conditions: gradient elution: 18 min: 93% acetonitrile/7% water, 20 min: 87% acetonitrile/13% water; flow rate: 1 mL/min; 20 μ L of sample was injected.
A detector: an evaporative light detector; tube temperature: 115 ℃ is carried out; the gas flow rate is 2L/min.
FIG. 3 is a diagram of the separation of 10 kinds of small molecular saccharides on an amphiphilic silica gel chromatographic packing modified by norbornene methylene imidazole hexafluorophosphate ionic liquid. Wherein, 1-D-ribose, 2-xylose, 3-DL-arabinose, 4-D-fructose, 5-glucose, 6-sucrose, 7-maltose, 8-lactose, 9-D-melezitose and 10-raffinose. As can be seen from FIG. 3, the high performance liquid chromatography packing prepared by the invention has good separation effect on small molecular sugar.
Drawings
FIG. 1 is a schematic diagram of the synthesis of the amphiphilic ionic liquid modified silica gel chromatographic packing of the invention.
FIG. 2 is an infrared characterization diagram of the amphiphilic ionic liquid modified silica gel chromatographic packing of the invention.
FIG. 3 is a graph of the separation of 10 small molecule sugars on an amphiphilic silica gel chromatographic packing.
Detailed Description
Example 1 Synthesis of amphiphilic Ionic liquid-modified silica gel chromatography Filler
(1) SiliconActivating glue: 6.0g of silica gel having a particle size of 5 μm (specific surface area 400 m)2G, pore volume 0.7cm3G, the aperture is 70 À), and the mixture is soaked in 12mol/L concentrated hydrochloric acid for 48 hours; taking out, centrifuging to remove concentrated hydrochloric acid solution, and centrifuging and washing with deionized water for multiple times until the supernatant is neutral; washed again by centrifugation with methanol, dehydrated and dried under vacuum at 72 ℃ for about 12 hours.
(2) Preparation of aminopropyl silica gel: 5g of activated silica gel was dispersed in 40ml of anhydrous toluene, 5ml (5.2 g) of aminopropyltriethoxysilane was added, mixed, refluxed at 130 ℃ for 48 hours under magnetic stirring, centrifuged to remove the solvent and unreacted substances, the solid was washed with toluene, ethanol and methanol in this order by centrifugation, and then dried under vacuum at 120 ℃ for 12 hours to obtain aminopropylsilica gel.
(3) Preparation of amide silica gel: into a 250ml three-necked flask was charged 3.83g (10 mmol) of sodium borate tetradecahydrate (Na)2B4O7·10H2O) and 100ml of distilled water are stirred for 30min under the protection of nitrogen; after the sodium borate is completely dissolved, 4.51g of dry aminopropyl silica gel is added, the mixture is stirred for 20min under the protection of nitrogen, and 3.39g (32 mmol) of anhydrous sodium carbonate is added, so that the pH value of the reaction mixed solution is approximately equal to 9-10. Then under the ice water bath, 1.24ml of 2-bromine isobutyryl bromide is slowly added by a syringe, nitrogen is protected, and after 24 hours of reaction at 25 ℃, the color of the mixed solution is changed from pink to yellow brown. The pH was maintained at approximately 9-10 throughout the reaction by adjusting the solution with anhydrous sodium carbonate. After the reaction, the solution pH =2 was adjusted with 6mol/L hydrochloric acid under cooling in an ice water bath, and the solid was centrifugally washed three times with 100ml of ethyl acetate, washed with saturated brine, and dried in vacuo at 60 ℃ to obtain about 4.47g of pale yellow amide silica gel.
(4) The synthesis of norbornene methylene bromide comprises the following steps:
a. synthesis of norbornene methylene bromide (NM-Br): 30 ml of dicyclopentadiene (224 mmol), 58ml of allyl bromide (672 mmol) and 200 mg of hydroquinone are mixed and stirred for 10 min, and then transferred to a 100ml autoclave with a polytetrafluoroethylene lining for reaction for 15 h at 180 ℃. And (3) distilling at 100 ℃ to remove excessive allyl bromide, and performing reduced pressure distillation on the residual oily liquid to collect 112 ℃ fractions, wherein the fractions are colorless liquid 61.2 g, and the yield is about 71%.
B, synthesis of NM-MIm-Br ionic liquid: taking 6.15 g (75 mmol) of freshly distilled methylimidazole and 9.35 g (50 mmol) of norbornene methylene bromide, carrying out a reaction for 24h at 75 ℃ under the protection of nitrogen to obtain black brown viscous liquid, washing off unreacted methylimidazole by using diethyl ether, washing off unreacted norbornene bromide by using n-hexane, and carrying out column chromatography separation to obtain 9.98 g of colorless liquid, wherein the yield is about 73.99%.
And c, synthesizing NM-MIm-PF6 ionic liquid: 3.20 g (12 mmol) of NM-MIm-Br ionic liquid is put into a 50ml round bottom flask, then 2.94 g (18 mmol) of ammonium hexafluorophosphate is added, distilled water is used as a solvent, the reaction is stirred at normal temperature for 10 hours, obvious layering is found after the reaction is finished, an oil phase is extracted by dichloromethane, dichloromethane extract is washed by distilled water for 3 times, anhydrous magnesium sulfate is dried, the solvent is removed by distillation under reduced pressure to obtain viscous liquid, and the liquid is separated by column chromatography to obtain 2.43 g of colorless viscous liquid, wherein the yield is about 75.68%.
(5) Preparing the polynorbornene methylene imidazole hexafluorophosphate ionic liquid modified silica gel by the ROMP technology: adding 5ml of dichloromethane and 10mg of Grubbs catalyst into 3g of ATRP initiator modified silica gel under the protection of argon, after reacting for 20min, washing off excessive Grubbs catalyst by using dichloromethane, adding 0.37g of dichloromethane solution (with the concentration of 0.25mol/L and 4ml of solvent) of norbornene methylene imidazole hexafluorophosphate ionic liquid (NM-MIm-PF6) monomer, and reacting for 2h at room temperature under the protection of argon to obtain polymer modified P (NM-MIm-PF6) silica gel.
(6) Preparation of amphiphilic ionic liquid modified silica gel chromatographic packing: stirring a hydrophilic monomer (such as poly (ethylene glycol) methacrylate OEGMA) (0.6 g) methanol/water solution (2.5 ml, volume ratio of 1: 4) with a certain concentration under the protection of nitrogen for 20min, sequentially adding cuprous bromide 4.1mg and 2, 2-bipyridine 16mg, stirring for 20min, adding into the polymer-modified silica gel, and reacting at normal temperature for 4h to obtain P (NM-MIm-PF6) -POEGMA binary modified silica gel (P (NM-MIm-PF6) -SiO 2-POEGMA).
Example 2 establishment of high liquid chromatography and detection of Small molecule sugars
Preparation of analytical samples: 1mg of D-ribose, xylose, DL-arabinose, D-fructose, glucose, sucrose, maltose, lactose, D-melezitose and raffinose are respectively dissolved in 1ml of water and then mixed.
Chromatographic packing: the amphiphilic ionic liquid prepared in example 1 modifies silica gel chromatography packing.
Mobile phase: acetonitrile-water; the flow rate is 1 mL/min; 20 μ L of injection (150X 4.6mm I.D.).
Elution conditions: gradient elution: 18 min: 93% acetonitrile/7% water, 20 min: 87% acetonitrile/13% water;
a detector: an evaporative light detector; tube temperature: 115 ℃ is carried out; gas flow rate: 2L/min, flow rate: 1 mL/min.
FIG. 2 is a separation diagram of 10 kinds of small molecular saccharides on an amphiphilic silica gel chromatographic packing modified by norbornene methylene imidazole hexafluorophosphate ionic liquid. Therefore, the high performance liquid chromatography packing has a good separation effect on micromolecular sugar.
Claims (10)
1. A preparation method of silica gel chromatographic packing modified by amphiphilic ionic liquid comprises the following steps:
(1) activation of silica gel: acidifying porous spherical silica gel for chromatography with hydrochloric acid, washing with water to neutrality, washing with methanol, and vacuum drying to obtain activated silica gel;
(2) preparation of aminopropyl silica gel: adding activated silica gel into anhydrous toluene, adding aminopropyl trimethoxysilane, and stirring and refluxing for 45-48 hours at 120-130 ℃; centrifugally washing and vacuum drying the product to obtain aminopropyl silica gel;
(3) preparation of amide silica gel: under the protection of nitrogen, sodium borate tetradecahydrate is used as a catalyst, and aminopropyl silica gel and 2-bromoisobutyryl bromide are stirred and refluxed for 10-12 hours at the temperature of 20-25 ℃ in a weak alkaline solution; washing the product with ethyl acetate and saturated salt solution in sequence, and drying in vacuum to obtain amide silica gel;
(4) preparation of polymerized ionic liquid modified silica gel: in dichloromethane, under the protection of argon and the action of a Grubbs catalyst, performing ring opening metathesis polymerization on the acyl bromide group-containing silica gel and the norbornene methylimidazole hexafluorophosphate ionic liquid at the temperature of 20-25 ℃ for 1.8-2 h; washing and drying the reaction product to obtain silica gel modified by the polymeric ionic liquid;
(5) preparation of silica gel chromatographic packing modified by amphiphilic ionic liquid: under the protection of nitrogen, sequentially adding cuprous bromide and 2, 2-bipyridyl into a methanol-water mixed solution of a hydrophilic monomer poly (ethylene glycol) methacrylate, uniformly stirring, adding silica gel modified by a polymeric ionic liquid, uniformly mixing, and carrying out an ATRP reaction at room temperature for 3.5-4 h; washing and drying the reaction product to obtain the silica gel chromatographic packing modified by the amphiphilic ionic liquid.
2. The method for preparing the amphiphilic ionic liquid modified silica gel chromatographic packing as claimed in claim 1, wherein the method comprises the following steps: in the step (1), the hydrochloric acid acidification treatment of the silica gel is to soak the silica gel in a concentrated hydrochloric acid solution with the concentration of 10-12 mol/L for 45-48 h.
3. The method for preparing the amphiphilic ionic liquid modified silica gel chromatographic packing as claimed in claim 1, wherein the method comprises the following steps: in the step (2), the mass ratio of the silica gel to the aminopropyltrimethoxysilane is 1: 1-1: 1.1.
4. The method for preparing the amphiphilic ionic liquid modified silica gel chromatographic packing as claimed in claim 1, wherein the method comprises the following steps: in the step (3), the mass-to-volume ratio of aminopropyl silica gel to 2-bromoisobutyryl bromide is 3.5: 1-3.6: 1 g/mL.
5. The method for preparing the amphiphilic ionic liquid modified silica gel chromatographic packing as claimed in claim 1, wherein the method comprises the following steps: in the step (4), the mass ratio of the acyl bromide group-containing silica gel to the norbornene methylene imidazole hexafluorophosphate ionic liquid is 1: 0.12-1: 0.14.
6. The method for preparing the amphiphilic ionic liquid modified silica gel chromatographic packing as claimed in claim 1, wherein the method comprises the following steps: in the step (4), the using amount of the Grubbs catalyst is 3-4% of the mass of the acyl bromide group-containing silica gel.
7. The method for preparing the amphiphilic ionic liquid modified silica gel chromatographic packing as claimed in claim 1, wherein the method comprises the following steps: in the step (5), the volume ratio of methanol to water in the methanol-water mixed solution is 1: 3.5-1: 4.
8. The method for preparing the amphiphilic ionic liquid modified silica gel chromatographic packing as claimed in claim 1, wherein the method comprises the following steps: in the step (5), the addition amount of the cuprous bromide is 0.6-0.7% of the mass of the hydrophilic monomer poly (ethylene glycol) methacrylate.
9. The method for preparing the amphiphilic ionic liquid modified silica gel chromatographic packing as claimed in claim 1, wherein the method comprises the following steps: in the step (5), the adding amount of the 2, 2-bipyridyl is 2-3% of the mass of the hydrophilic monomer methacrylic acid poly (ethylene glycol) ester.
10. The amphiphilic ionic liquid modified silica gel chromatographic packing prepared by the method of claim 1 is used for detecting and separating small molecular sugar.
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| CN102101043A (en) * | 2009-12-18 | 2011-06-22 | 中国科学院兰州化学物理研究所 | Method for preparing polyvinyl imidazole type silica gel filler |
| CN104415740A (en) * | 2013-09-04 | 2015-03-18 | 北京蛋白质组研究中心 | Hydrophilic chromatographic packing as well as preparation method and application thereof |
| CN104925816A (en) * | 2015-06-24 | 2015-09-23 | 齐鲁工业大学 | Titanium dioxide modified rod-shaped silicon dioxide nuclear shell material and preparation method thereof |
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| CN102101043A (en) * | 2009-12-18 | 2011-06-22 | 中国科学院兰州化学物理研究所 | Method for preparing polyvinyl imidazole type silica gel filler |
| CN104415740A (en) * | 2013-09-04 | 2015-03-18 | 北京蛋白质组研究中心 | Hydrophilic chromatographic packing as well as preparation method and application thereof |
| CN104925816A (en) * | 2015-06-24 | 2015-09-23 | 齐鲁工业大学 | Titanium dioxide modified rod-shaped silicon dioxide nuclear shell material and preparation method thereof |
| CN105536747A (en) * | 2016-01-14 | 2016-05-04 | 重庆大学 | Intelligent response liquid chromatogram filling material and preparation method thereof |
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