CN112843790A - Application of mesoporous carbon material as chromatographic packing in chromatographic column - Google Patents

Application of mesoporous carbon material as chromatographic packing in chromatographic column Download PDF

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Publication number
CN112843790A
CN112843790A CN201911191095.9A CN201911191095A CN112843790A CN 112843790 A CN112843790 A CN 112843790A CN 201911191095 A CN201911191095 A CN 201911191095A CN 112843790 A CN112843790 A CN 112843790A
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chromatographic
mesoporous carbon
core
use according
acid
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CN201911191095.9A
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吴仁安
赵兴云
张红燕
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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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
    • B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
    • B01D15/22—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the construction of the column
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
    • B01J20/282—Porous sorbents
    • B01J20/283—Porous sorbents based on silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G01N30/08—Preparation using an enricher
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/60—Construction of the column

Abstract

The invention discloses an application of a mesoporous carbon material as a chromatographic packing in a chromatographic column, which takes silicon dioxide microspheres as a core, a pore-expanding agent and a carbon source react under certain conditions and are coated on the surface of the core, and then the material is washed, dried and calcined in situ in high-temperature inert atmosphere to obtain a material with microsphere silicon dioxide particles as the core and a carbon material as a shell. The method adopted by the invention can realize controllable adjustment of the aperture and the thickness through the parameters of the pore-expanding agent concentration and the carbon source concentration, and the obtained material as a chromatographic packing can be applied to the fields of sample pretreatment capture, liquid chromatographic separation, enrichment and extraction of organic matters in water and the like in a chromatographic column.

Description

Application of mesoporous carbon material as chromatographic packing in chromatographic column
Technical Field
The invention relates to the field of separation and enrichment of complex samples, in particular to application of a material containing a mesoporous carbon structure as a chromatographic packing in enrichment, separation and analysis of complex samples such as polypeptide and the like in a chromatographic column.
Background
Carbon materials have been the focus of research in the field of separation and analytical chemistry, and many carbon materials such as graphene, graphene oxide, reduced graphene, carbon nanotubes, etc. have been reported to be widely applied to the pretreatment analysis of complex samples. (analytical Chimica Acta 734(2012) 1-30; anal. chem.2014,86,4,2246-
Qin et al reported that mesoporous carbon materials were used for the enrichment of endogenous polypeptides in serum, and by using the size exclusion effect and hydrophobic effect, they were well enriched, and 3402 endogenous peptide fragments were identified from 20. mu.l of serum (Angew. chem. int. Ed.2011,50, 12218-. Qin et al reported that highly ordered mesoporous carbon material O-CMK can identify and analyze the structure of sugar chain in glycoprotein (anal. chem.2011,83, 7721-7728). Then, compared with O-CMK, the silicon-carbon mesoporous composite material MCM-C developed by the method has the characteristics of high specific surface area and short channel length, and can quickly complete the adsorption and desorption of sugar chains. (chem. commun.,2013,49, 5162-5164) however these works were mainly for off-line sample processing analysis. And is not used in chromatographic columns for chromatographic packing.
The invention discloses application of a mesoporous carbon material as a chromatographic packing in a chromatographic column, and is also used for online enrichment analysis of complex samples.
Disclosure of Invention
The invention aims to provide an application of a mesoporous carbon material as a chromatographic packing in a chromatographic column. In order to achieve the purpose, the invention provides the following technical scheme: (1) firstly, taking a silicon dioxide microsphere as a seed inner core, and coating a layer of cross-linked polymer outer layer on the surface of the microsphere;
(2) and (3) carbonizing the surfactant and the polymer in situ in the core-shell material obtained in the step to obtain the core-shell material with the silicon dioxide microspheres as the inner core and the mesoporous carbon as the outer shell.
(3) The filler is filled in a capillary column or a stainless steel column for online enrichment and separation of complex samples.
As a preferable scheme, no pore-expanding agent, such as one or more of benzene, trimethylbenzene, C18-C30 long-chain alkane, C18-C30 long-chain alcohol, ionic surfactant and nonionic surfactant, is or may be added into the preparation system of the crosslinked polymer in the step (1).
As a preferable mode, the organic compound carbon source crosslinking reaction in the step (1) may use a catalyst: hydrochloric acid, sulfuric acid, nitric acid, acetic acid, potassium hydroxide, sodium hydroxide, ammonia water, phosphate and acetate.
As a preferred scheme, the in-situ carbonization condition of the step (2) is high-temperature calcination under a protective atmosphere; wherein, the calcining temperature is 400-2400 ℃, preferably 600-1200 ℃; the protective atmosphere is one or more of nitrogen, helium, neon, argon, krypton or xenon.
As a preferable mode, the organic compound of step (1) may be urea, melamine, cyanuric acid, phenol and substituted phenols such as m-aminophenol, m-mercaptophenol, 3-hydroxyphenylboronic acid, 3-hydroxybenzoic acid; and one or more of formaldehyde, acetaldehyde or hexamethylenetetramine;
a crosslinked polymer formed from the organic compound after mixing at a temperature in the range of 20 to 260 degrees celsius, preferably 40 to 90 degrees celsius.
The invention has the beneficial effects that:
1. the chromatographic packing is filled in a capillary column or a stainless steel column to prepare a chromatographic column, and further can be used for online enrichment and separation analysis of complex samples.
2. The mesoporous carbon material with the nanoscale is coated on the surface of the mesoporous silica gel, so that the defects of overhigh pressure and short service life of the mesoporous carbon as a chromatographic packing are overcome.
3. The method of the invention provides a choice for large-scale purification and preparation of compounds such as saccharides or polypeptides.
4. The thickness of the mesoporous carbon can be determined by adjusting the dosage of the carbon source;
5. the graphitization degree of the mesoporous carbon can be adjusted by the calcination temperature;
6. the aperture and specific surface area of the mesoporous carbon can be adjusted by a surfactant and a pore-expanding agent.
Drawings
FIG. 1 shows an optical microscopy characterization of a starting silica microsphere;
FIG. 2 is a representation of the optical microscope after the mesoporous carbon material modifies the silica.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. The experimental procedures used in the following examples are all conventional procedures unless otherwise specified. Materials, reagents and the like used in the following examples are commercially available unless otherwise specified, and should be understood. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention.
Example 1:
0.25g of SiO2(pore diameter 4nm, specific surface area 170 m)2And/g), 0.04g of hexadecyl trimethyl ammonium bromide, 100ml of a mixture of water and ethanol (volume ratio is 1:20), adding the mixture into a 250ml three-neck flask, adding 100ul of ammonia water with the mass concentration of 20%, uniformly dispersing, mechanically stirring for 30 minutes, slowly adding melamine, and continuously stirring and reacting in a water bath at 60 ℃ for 8 hours. And taking the material out, treating the material at 1200 ℃ for 1h, and cleaning and drying the material to obtain a solid product. Mesoporous carbon chromatographic packing (aperture 3nm, specific surface area 150 m)2/g)
The solid product is then packed in a chromatographic column and the polypeptide is analyzed under loading conditions where the acetonitrile to water ratio is less than 40% and under elution conditions where the acetonitrile to water ratio is greater than 40%. The target polypeptide can be extracted and analyzed.
Example 2:
0.5g of SiO2(pore diameter 10nm, specific surface area 300 m)2And/g), 0.04g of hexadecyltrimethylammonium chloride, 100ml of a mixture of water and ethanol (volume ratio is 1:10), adding the mixture into a 250ml three-neck flask, adding 100ul of ammonia water with the mass concentration of 26%, uniformly dispersing, mechanically stirring for 30 minutes, slowly adding formaldehyde, and continuously stirring and reacting in a water bath at 60 ℃ for 8 hours. Taking out the material, cleaning, drying, taking out the material, and treating at 1000 deg.C for 1h to obtain mesoporous carbon chromatographic packingMaterial (pore diameter 9nm, specific surface area 210 m)2/g)。
Example 3:
0.75g of SiO2(pore size 12nm, specific surface area 330m20.04g of octadecyl trimethyl ammonium bromide, 100ml of a mixture of water and ethanol (volume ratio is 1:5), adding the mixture into a 250ml three-neck flask, adding 100ul (mass concentration is 27%) of ammonia water, dispersing uniformly, mechanically stirring for 30 minutes, adding formaldehyde, and continuously stirring and reacting in a water bath at 60 ℃ for 8 hours. And (3) taking out the material, cleaning and drying the material, and treating the material at 800 ℃ for 1h to obtain the mesoporous carbon chromatographic packing (the thickness of the mesoporous carbon is 10 nanometers).
Example 4:
1g of SiO2(pore diameter 30nm, specific surface area 180 m)2And/g), 0.04g of octadecyl trimethyl ammonium chloride, 100ml of a mixture of water and ethanol in a volume ratio of 1:2), adding the mixture into a 250ml three-neck flask, adding 120ul (28 mass percent) of ammonia water, uniformly dispersing, mechanically stirring for 30 minutes, slowly adding cyanuric chloride, and continuously stirring in a water bath at 60 ℃ for reaction for 8 hours. And (3) taking out the material, cleaning and drying the material, taking out the material, and treating the material at 1100 ℃ for 1h to obtain the mesoporous carbon chromatographic packing (the thickness of the shell layer is 20 nm).
Example 5:
1g of SiO2(pore diameter 50nm, specific surface area 140 m)20.04g of octadecyl trimethyl ammonium chloride, 100ml of mixture of water and ethanol with the volume ratio of 2:1), adding the mixture into a 250ml three-neck flask, adding 80ul (25 percent by mass) of ammonia water, uniformly dispersing, mechanically stirring for 30 minutes, slowly adding glyoxal, and continuously stirring and reacting in a water bath at 60 ℃ for 8 hours. Taking out the material, cleaning, drying, treating at 900 deg.C for 1 hr to obtain mesoporous carbon chromatographic filler (with pore diameter of 40nm and specific surface area of 130 m)2/g)。
Example 6:
2g of SiO2(pore diameter 80nm, specific surface area 140 m)2/g), 0.04g of octadecyl trimethyl ammonium chloride, 100ml of a mixture of water and ethanol in a volume ratio of 10:1), added into a 500ml three-necked flask, added with 0.2g of fluorophenol, added with 150ul of ammonia water (mass concentration of 28%), dispersed uniformly, and mechanically stirredStirring for 60 minutes, slowly adding hexamethylene tetramine, and continuously stirring and reacting for 8 hours in a water bath at the temperature of 60 ℃. Taking out the material, cleaning, drying, treating at 600 deg.C for 3 hr to obtain mesoporous carbon chromatographic packing (aperture 60nm, specific surface area 210 m)2/g)。
The application embodiment is as follows: the mesoporous carbon chromatographic packing is applied to a chromatographic column, and compounds such as saccharides, polypeptides and the like are well separated under the condition of a reverse phase chromatographic mobile phase.
Finally, it is also noted that the above-mentioned lists merely illustrate a few specific embodiments of the invention. It is obvious that the invention is not limited to the above embodiments, but that many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.

Claims (9)

1. The application of the mesoporous carbon material as chromatographic packing in a chromatographic column is characterized in that: the silica microspheres are used as inner cores, and the mesoporous carbon is used as the chromatographic packing of the outer layer.
2. Use according to claim 1, characterized in that: the inner core is silicon dioxide microsphere with particle size of 1-100 microns, including one or two of solid silicon sphere and porous silicon sphere, the pore size distribution of the porous silicon sphere is 1nm-300nm, preferably 10nm-100nm, and the porosity is 0.01-2, preferably 0.1-1.
3. Use according to claim 1 or 2, characterized in that: the mesoporous carbon layer attached to the outer portion of the inner core has a pore size distribution of 0.1nm to 300nm, preferably 1nm to 100nm, a porosity of 0.01 to 2, preferably 0.1 to 2, and a thickness of 0.01nm to 1000nm, preferably 1 to 100 nm.
4. Use according to any one of claims 1 to 3, characterized in that the chromatographic packing is prepared by the following steps:
(1) taking silicon dioxide microspheres as seeds, and taking an organic compound as a carbon source to perform a crosslinking reaction on the surfaces of the microspheres to prepare a core-shell material taking the silicon dioxide microspheres as an inner core and a crosslinked polymer as a shell;
(2) and (3) carbonizing the crosslinked polymer in the core-shell material obtained in the step in situ to prepare the core-shell chromatographic material compounded by the silicon dioxide microsphere material and the mesoporous carbon material.
5. The use according to claim 4, wherein the polymer cross-linked in step (1) is prepared without or with addition of pore-expanding agent, such as one or more of benzene, trimethylbenzene, C18-C30 long-chain alkane, C18-C30 long-chain alcohol, ionic surfactant and nonionic surfactant.
6. Use according to claim 2, characterized in that: the organic compound carbon source crosslinking reaction described in the step (1) may use a catalyst: hydrochloric acid, sulfuric acid, nitric acid, acetic acid, potassium hydroxide, sodium hydroxide, ammonia water, phosphate and acetate.
7. The use of claim 4, wherein the in-situ carbonization conditions in step (2) are high-temperature calcination under a protective atmosphere; wherein, the calcining temperature is 400-2400 ℃, preferably 600-1200 ℃; the protective atmosphere is one or more of nitrogen, helium, neon, argon, krypton or xenon.
8. The use of claim 4, wherein the organic compound of step (1) is selected from urea, melamine, cyanuric acid, phenol and substituted phenols, such as m-aminophenol, m-mercaptophenol, 3-hydroxyphenylboronic acid, 3-hydroxybenzoic acid; and one or more of formaldehyde, acetaldehyde or hexamethylenetetramine; a crosslinked polymer formed from the organic compounds after mixing at a temperature in the range of 20 to 260, preferably 40 to 90 degrees celsius.
9. Use according to claim 1, characterized in that the chromatographic column is prepared as follows:
the chromatographic packing is filled in a capillary column or a stainless steel column to prepare a chromatographic column, and further can be used for online enrichment and separation analysis of complex samples.
CN201911191095.9A 2019-11-28 2019-11-28 Application of mesoporous carbon material as chromatographic packing in chromatographic column Pending CN112843790A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030153636A1 (en) * 2002-02-12 2003-08-14 Steven Dietz Mesoporous carbons and polymers from hydroxylated benzenes
US20130112605A1 (en) * 2010-07-26 2013-05-09 Waters Technologies Corporation Superficially porous materials comprising a substantially nonporous core having narrow particle size distribution; process for the preparation thereof; and use thereof for chromatographic separations
CN106955679A (en) * 2017-03-15 2017-07-18 华东理工大学 Hud typed filler of analysis and preparation method thereof is separated applied to liquid chromatogram
CN107694491A (en) * 2016-08-08 2018-02-16 上海复元纳米介孔材料有限责任公司 A kind of core shell structure complex microsphere and its production and use
CN110075770A (en) * 2019-05-11 2019-08-02 复旦大学 Magnetic order mesoporous carbon-based or polymer-based core-shell structure microballoon and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030153636A1 (en) * 2002-02-12 2003-08-14 Steven Dietz Mesoporous carbons and polymers from hydroxylated benzenes
US20130112605A1 (en) * 2010-07-26 2013-05-09 Waters Technologies Corporation Superficially porous materials comprising a substantially nonporous core having narrow particle size distribution; process for the preparation thereof; and use thereof for chromatographic separations
CN107694491A (en) * 2016-08-08 2018-02-16 上海复元纳米介孔材料有限责任公司 A kind of core shell structure complex microsphere and its production and use
CN106955679A (en) * 2017-03-15 2017-07-18 华东理工大学 Hud typed filler of analysis and preparation method thereof is separated applied to liquid chromatogram
CN110075770A (en) * 2019-05-11 2019-08-02 复旦大学 Magnetic order mesoporous carbon-based or polymer-based core-shell structure microballoon and preparation method thereof

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Application publication date: 20210528