CN116272920B - Triazine covalent organic framework modified silicon sphere novel stationary phase high performance liquid chromatography packing and preparation method and application thereof - Google Patents
Triazine covalent organic framework modified silicon sphere novel stationary phase high performance liquid chromatography packing and preparation method and application thereof Download PDFInfo
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- CN116272920B CN116272920B CN202310228313.1A CN202310228313A CN116272920B CN 116272920 B CN116272920 B CN 116272920B CN 202310228313 A CN202310228313 A CN 202310228313A CN 116272920 B CN116272920 B CN 116272920B
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- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 87
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000004128 high performance liquid chromatography Methods 0.000 title claims abstract description 66
- 238000012856 packing Methods 0.000 title claims abstract description 59
- 230000005526 G1 to G0 transition Effects 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 59
- 239000010703 silicon Substances 0.000 claims abstract description 59
- 150000003376 silicon Chemical class 0.000 claims abstract description 37
- WSULSMOGMLRGKU-UHFFFAOYSA-N 1-bromooctadecane Chemical compound CCCCCCCCCCCCCCCCCCBr WSULSMOGMLRGKU-UHFFFAOYSA-N 0.000 claims abstract description 27
- -1 1,3, 5-tris (4-aminophenyl) benzene triazine Chemical compound 0.000 claims abstract description 12
- AEKQNAANFVOBCU-UHFFFAOYSA-N benzene-1,3,5-tricarbaldehyde Chemical compound O=CC1=CC(C=O)=CC(C=O)=C1 AEKQNAANFVOBCU-UHFFFAOYSA-N 0.000 claims abstract description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 72
- 239000000463 material Substances 0.000 claims description 68
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 63
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 33
- 239000003153 chemical reaction reagent Substances 0.000 claims description 33
- 238000002444 silanisation Methods 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000000377 silicon dioxide Substances 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 22
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 19
- 238000001914 filtration Methods 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims description 16
- 238000001291 vacuum drying Methods 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 238000006884 silylation reaction Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 239000012043 crude product Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 8
- 239000002262 Schiff base Substances 0.000 claims description 8
- 150000004753 Schiff bases Chemical class 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- FVJFRFUSHCIRKP-UHFFFAOYSA-N disodium;hydrogen borate Chemical compound [Na+].[Na+].OB([O-])[O-] FVJFRFUSHCIRKP-UHFFFAOYSA-N 0.000 claims description 8
- 238000005191 phase separation Methods 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical group C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- 150000001448 anilines Chemical class 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 238000005576 amination reaction Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 229910021426 porous silicon Inorganic materials 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 description 24
- 230000014759 maintenance of location Effects 0.000 description 15
- 238000000926 separation method Methods 0.000 description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 238000005303 weighing Methods 0.000 description 9
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 8
- 150000004996 alkyl benzenes Chemical class 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- 230000007246 mechanism Effects 0.000 description 5
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthene Chemical compound C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 4
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 3
- 239000008213 purified water Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OIAQMFOKAXHPNH-UHFFFAOYSA-N 1,2-diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC=C1C1=CC=CC=C1 OIAQMFOKAXHPNH-UHFFFAOYSA-N 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 2
- XJKSTNDFUHDPQJ-UHFFFAOYSA-N 1,4-diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=C(C=2C=CC=CC=2)C=C1 XJKSTNDFUHDPQJ-UHFFFAOYSA-N 0.000 description 2
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229930184652 p-Terphenyl Natural products 0.000 description 2
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 125000005580 triphenylene group Chemical group 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 238000005251 capillar electrophoresis Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a triazine covalent organic framework modified silicon ball novel stationary phase high performance liquid chromatography packing, and a preparation method and application thereof, and belongs to the technical field of high performance liquid chromatography packing preparation. According to the invention, the triazine covalent organic framework synthesized by 1,3, 5-tris (4-aminophenyl) benzene triazine and 1,3, 5-benzene trialdehyde is bonded on the surface of the silicon sphere, and then bromooctadecane is embedded on the covalent organic framework to obtain the brand-new high-performance liquid chromatography packing.
Description
Technical Field
The invention belongs to the technical field of preparation of high performance liquid chromatography fillers, and relates to a novel stationary phase high performance liquid chromatography filler of triazine covalent organic framework modified silica spheres, and a preparation method and application thereof.
Background
Chromatographic stationary phases are the most important part of high performance liquid chromatography systems, and development of new stationary phases has been an important direction in high performance liquid chromatography research. The traditional preparation method of the packed chromatographic column stationary phase is to select silica gel or metal oxide with a porous structure as a framework and modify functional groups to provide separation selectivity, but most of the stationary phases have the defects of high column pressure, poor separation selectivity and the like. In order to meet the requirements of high selectivity and high sensitivity in the analysis of complex samples, the development of a novel chromatographic stationary phase with high separation efficiency and good selectivity has become a hot spot in research in the field of separation science. The Covalent Organic Framework (COF) material is an emerging crystalline porous material consisting of light element covalent bonds with periodic frameworks and ordered pores, has the advantages of low density, large specific surface area, high chemical stability and the like, and is widely applied to the fields of solid phase extraction, sensing, chromatography, capillary electrophoresis, catalysis and the like. In view of the above advantages, the COF material has a hydrophobic effect, pi-pi interaction and size selectivity on target analytes, has the potential to prepare a high performance liquid chromatography stationary phase, is a powerful tool for separating and analyzing various compounds, can provide various acting forces on the retention of solute molecules in separation and analysis, can perform separation according to different characteristics of analysis substances, improves separation selectivity, and is suitable for separation and analysis on complex samples.
Accordingly, attempts have been made to prepare high performance liquid chromatography packing using a valuable organic framework (COF) material.
Disclosure of Invention
In view of the above, one of the purposes of the present invention is to provide a triazine covalent organic framework modified silica sphere novel stationary phase high performance liquid chromatography packing; the second purpose of the invention is to provide a preparation method of triazine covalent organic framework modified silica sphere novel stationary phase high performance liquid chromatography packing; the invention further aims to provide an application of the triazine covalent organic framework modified silica sphere novel stationary phase high performance liquid chromatography packing serving as a stationary phase in high performance liquid chromatography reversed phase separation.
In order to achieve the above purpose, the present invention provides the following technical solutions:
1. The triazine covalent organic framework modified silica sphere novel stationary phase high performance liquid chromatography packing comprises silica spheres bonded with a silanization reagent, a covalent organic framework material bonded with the surface of the silica spheres bonded with the silanization reagent and an embedded carbon-eighteen chain on the covalent organic framework material;
The covalent organic framework material is an amino bonding material obtained by reacting triazine covalent organic framework, 1,3, 5-benzene trialdehyde and a silanization reagent through Schiff base.
2. The preparation method of the high performance liquid chromatography packing comprises the following steps:
(1) Silicon sphere surface modification initiator: activating the porous silicon spheres by using acid to obtain activated silicon spheres, and then carrying out amination treatment on the surfaces of the silicon spheres by using a silylation reagent to obtain silicon spheres bonded with the silylation reagent;
(2) And bonding triazine covalent organic framework materials on the surface of the silicon sphere bonded with the silanization reagent: carrying out Schiff base reaction on 1,3, 5-tris (4-aminophenyl) benzene triazine and 1,3, 5-benzene trialdehyde and the silicon spheres bonded with the silylation agent obtained in the step (1) to generate an amino bonding material, namely bonding a covalent organic framework material on the surfaces of the silicon spheres bonded with the silylation agent;
(3) Embedding carbon eighteen chains on the triazine covalent organic framework material: and 2) carrying out chemical reaction on bromooctadecane and the silicon spheres with the surface bonded with the triazine covalent organic framework material obtained in the step 2), and embedding carbon octadeca chains on the covalent organic framework material to obtain the Schiff base covalent organic framework modified silicon sphere novel stationary phase high performance liquid chromatography packing.
Preferably, in the step (1), the porous silicon spheres have a particle diameter of 2 to 10 μm and a pore diameter
Preferably, in the step (1), the specific method of the amination treatment is as follows: firstly, ultrasonically suspending the activated silicon spheres by toluene, adding a silanization reagent, reacting for 3-24 hours at the temperature of 100-120 ℃ under the protection of nitrogen, filtering and cleaning by absolute ethyl alcohol after the reaction is finished, and vacuum drying for 5-24 hours at normal temperature or for 2-10 hours at 50-100 ℃ to obtain the silicon spheres bonded with the silanization reagent;
the silylating agent is 3-aminopropyl triethoxysilane;
The mass molar ratio of the activated silicon spheres to the silanization reagent is 1.5-3:8-15, g: mmol;
The activated silicon spheres are prepared according to the following method: adding the silicon spheres into hydrochloric acid solution with the concentration of 1mol/L according to the mass-volume ratio of 1:30 and g/mL, stirring for 3-5h at 90-100 ℃, filtering, washing with water to be neutral, and drying for 5-24 h at 50-100 ℃ to obtain the activated silicon spheres.
Preferably, in the step (2), the method for bonding triazine covalent organic framework material to the surface of the silicon sphere bonded with the silylation agent specifically comprises the following steps: adding an organic solvent into the silicon spheres bonded with the silylation agent prepared in the step (1) for dissolving to obtain a mixture I, then continuously adding 1,3, 5-tris (4-aminophenyl) benzene triazine and 1,3, 5-benzene trialdehyde to fully dissolve to obtain a mixed solution, adding an acetic acid solution, carrying out Schiff base reaction for 3-4 days in the environment of 120 ℃, filtering after the reaction is finished, washing with ethanol to obtain a crude product, fully reducing the crude product with a sodium hydrogen borate solution, and bonding triazine covalent organic framework materials on the surfaces of the silicon spheres bonded with the silylation agent after drying.
Further preferably, the mass ratio of the silicon spheres bonded with the silylating agent, the 1,3, 5-tris (4-aminophenyl) benzene triazine and the 1,3, 5-benzene trialdehyde is 0.5:90-91:40-41;
the organic solvent is 1, 4-dioxane;
The mass volume ratio of the silicon spheres bonded with the silanization reagent to the organic solvent is 1:50-60, g: mL;
The concentration of the acetic acid solution is 12mol/L, and the volume ratio of the acetic acid to the mixed solution is 1:12-15;
the concentration of the sodium hydrogen borate solution is 2%;
The mass volume ratio of the crude product to the sodium hydrogen borate solution is 1:20-25, g is mL;
The drying is normal temperature vacuum drying or vacuum drying for 10-24 h at 50-100 ℃.
Preferably, in the step (3), the method for embedding the carbon eighteen chains on the triazine covalent organic framework material specifically comprises the following steps: immersing 1-bromooctadecane in dry toluene according to the mass-volume ratio of 2-3:5-6 and g/ml to obtain a mixture II according to the following weight-volume ratio of 1: adding dry toluene to make it fully dissolved to obtain mixture III, adding the product prepared in step (2), adding triethylamine, making reaction for 20-24 hr under nitrogen atmosphere at 90-100 deg.C, filtering after reaction, respectively using dry toluene and ethyl alcohol to wash them clean, drying so as to obtain the invented product.
Further preferably, the mass ratio of the 1-bromooctadecane to the product prepared in the step (2) is 1:1, a step of;
the volume ratio of triethylamine to dry toluene added to mixture III was 1:99 to 100;
The drying is normal temperature vacuum drying or vacuum drying for 10-24 h at 50-100 ℃.
3. The high performance liquid chromatography packing is used as a stationary phase in high performance liquid chromatography reversed phase separation, wherein the type of compounds separated in the reversed phase separation is any one of alkylbenzene compounds, position isomer compounds, aniline compounds or polycyclic aromatic hydrocarbon compounds containing alkyl chain substitution of different numbers of carbon atoms.
The invention has the beneficial effects that: the invention discloses a triazine covalent organic framework modified silica sphere novel stationary phase high performance liquid chromatography packing, which is prepared by a method of bonding a triazine covalent organic framework material on the surface of a silica sphere bonded with a silanization reagent and embedding a carbon-eighteen chain on the triazine covalent organic framework, and comprises the silica sphere bonded with the silanization reagent, the triazine covalent organic framework material bonded with the surface of the silica sphere bonded with the silanization reagent and the high performance liquid chromatography packing of the carbon-eighteen chain embedded on the triazine covalent organic framework. On one hand, the high performance liquid chromatography packing has excellent physical structures such as high mechanical strength, good physical and chemical properties and the like of the silica gel packing, so that the high performance liquid chromatography packing can be applied in a reverse phase separation mode and has the advantages of high separation speed, high separation selectivity and the like; on the other hand, the preparation method of the high performance liquid chromatography packing is simple and easy to operate.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objects and other advantages of the invention may be realized and obtained by means of the instrumentalities and combinations particularly pointed out in the specification.
Drawings
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in the following preferred detail with reference to the accompanying drawings, in which:
FIG. 1 is an infrared spectrum of different substances, wherein a is bromooctadecane and triazine covalent organic framework material modified silica sphere novel stationary phase high performance liquid chromatography packing (Sil-COF-C18), b is silica sphere (Sil-COF) with surface bonded triazine covalent organic framework material, and C is silica sphere (Sil-APTES) with bonded silylation agent;
FIG. 2 is a thermogravimetric analysis of different substances, wherein a is silicon spheres (Silica), b is bromooctadecane and triazine covalent organic framework material modified silicon spheres novel stationary phase high performance liquid chromatography packing (Sil-COF-C18);
FIG. 3 is a chromatogram obtained after separating polycyclic aromatic hydrocarbon substances, wherein the polycyclic aromatic hydrocarbon substances corresponding to retention times at positions 1,2, 3 and 4 are naphthalene, fluorene, phenanthrene and fluoranthene respectively;
FIG. 4 is a chromatogram obtained after separation of alkylbenzene species, wherein the polycyclic aromatic hydrocarbon species corresponding to retention times at positions 1,2, 3, 4 and 5 are toluene, ethylbenzene, propylbenzene, butylbenzene, pentylene, respectively;
FIG. 5 is a chromatogram obtained after separating positional isomers, wherein the polycyclic aromatic hydrocarbon substances corresponding to retention times at positions 1,2 and 3 are p-terphenyl, o-terphenyl and triphenylene, respectively;
FIG. 6 is a chromatogram obtained after separating anilines, wherein the polycyclic aromatic hydrocarbon compounds corresponding to retention times at positions 1,2, 3, 4 and 5 are 1, 2-phenylenediamine, aniline, benzidine and 1-naphthylamine, respectively.
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention. It should be noted that the illustrations provided in the following embodiments merely illustrate the basic idea of the present invention by way of illustration, and the following embodiments and features in the embodiments may be combined with each other without conflict.
Example 1
Preparing a novel stationary phase high performance liquid chromatography packing (Sil-COF-C18) of a silicon sphere modified by a bromooctadecane and triazine covalent organic framework material, wherein the high performance liquid chromatography packing is the novel stationary phase high performance liquid chromatography packing of the silicon sphere modified by the bromooctadecane and triazine covalent organic framework material, and specifically comprises the following steps:
(1) Weighing 5g of silicon spheres (particle size of 2-10 μm and pore diameter of ) Adding 150mL of 1mol/L HCl solution, stirring at 90 ℃ for reaction for 3 hours, filtering, washing with purified water to be neutral, and drying at 80 ℃ for 24 hours to obtain activated silicon spheres (Silica);
(2) Weighing 3g of the activated silicon spheres (Silica) prepared in the step (1), adding the activated silicon spheres into toluene for ultrasonic suspension, adding 2mL (8.48 mmol) of 3-aminopropyl triethoxysilane (APTES), carrying out ultrasonic treatment until the activated silicon spheres are uniformly dispersed, stirring and refluxing for 24 hours under the conditions of 110 ℃ and nitrogen protection, filtering and washing the activated silicon spheres with absolute ethyl alcohol after the reaction is finished, and carrying out vacuum drying at 80 ℃ for 10 hours at normal temperature to obtain silicon spheres (Sil-APTES) bonded with a silanization reagent for later use;
(3) Weighing 0.5g of silicon spheres (Sil-APTES) bonded with the silanization reagent prepared in the step (2), placing in 30mL of 1, 4-dioxane, adding 40.5mg of 1,3, 5-benzene trialdehyde, 90.0mg of 1,3, 5-tris (4-aminophenyl) benzene triazine (TAPT), carrying out ultrasonic treatment until the mixture is uniformly dispersed, adding 1.6mL of acetic acid (AcOH) with the concentration of 12mol/L, stirring for 3 days at room temperature, washing with ethanol after the reaction is finished to obtain a crude product, fully reducing the crude product with 50mL of 2% sodium borate solution, and then carrying out vacuum drying at 60 ℃ for 24 hours to obtain silicon spheres (Sil-COF) with the surface bonded triazine covalent organic framework material;
(4) Immersing 2g of 1-bromooctadecane in 5ml of dry toluene according to the mass-volume ratio of 2:5, continuously adding 245ml of dry toluene to fully dissolve the mixture to obtain a mixture III, adding 2g of silicon spheres (Sil-COF) of the surface-bonded triazine covalent organic framework material prepared in the step (3), adding 2.5ml of triethylamine, reacting for 24 hours in a nitrogen environment at 90 ℃, filtering after the reaction is finished, washing the mixture with dry toluene and ethanol respectively, and drying to embed carbon octadeca chains on the triazine covalent organic framework material.
Example 2
Preparing a novel stationary phase high performance liquid chromatography packing (Sil-COF-C18) of a silicon sphere modified by a bromooctadecane and triazine covalent organic framework material, wherein the high performance liquid chromatography packing is the novel stationary phase high performance liquid chromatography packing of the silicon sphere modified by the bromooctadecane and triazine covalent organic framework material, and specifically comprises the following steps:
(1) Weighing 5g of silicon spheres (particle size of 2-10 μm and pore diameter of ) Adding 150mL of 1mol/L HCl solution, stirring at 100 ℃ for reaction for 5 hours, filtering, washing with purified water to neutrality, and drying at 50 ℃ for 24 hours to obtain activated silicon spheres (Silica);
(2) Weighing 1.5g of the activated silicon spheres (Silica) prepared in the step (1), adding the activated silicon spheres into toluene for ultrasonic suspension, adding 3.54mL (15 mmol) of 3-aminopropyl triethoxysilane (APTES), carrying out ultrasonic treatment until the activated silicon spheres are uniformly dispersed, stirring and refluxing for 3 hours under the conditions of 120 ℃ and nitrogen protection, filtering and washing the activated silicon spheres with absolute ethyl alcohol after the reaction is finished, and carrying out vacuum drying at 50 ℃ for 10 hours at normal temperature to obtain silicon spheres (Sil-APTES) bonded with a silanization reagent for later use;
(3) Weighing 0.5g of silicon spheres (Sil-APTES) bonded with the silanization reagent prepared in the step (2), placing in 25mL of 1, 4-dioxane, adding 40mg of 1,3, 5-benzene trialdehyde, 91.0mg of 1,3, 5-tris (4-aminophenyl) benzene triazine (TAPT), carrying out ultrasonic treatment until the mixture is uniformly dispersed, adding 1.6mL of acetic acid (AcOH) with the concentration of 12mol/L, stirring for 3 days at room temperature, washing with ethanol after the reaction is finished to obtain a crude product, fully reducing the crude product with 50mL of 2% sodium hydrogen borate solution, and then carrying out vacuum drying for 24 hours at 60 ℃ to obtain silicon spheres (Sil-COF) bonded with triazine covalent organic framework materials on the surfaces of the silicon spheres for standby;
(4) 2g of 1-bromooctadecane is immersed in 6ml of dry toluene to obtain a mixture II, 300ml of dry toluene is continuously added to fully dissolve the mixture to obtain a mixture III, 2g of silicon spheres (Sil-COF) of which the surfaces are bonded with triazine covalent organic framework materials prepared in the step (3) are added, 3.1ml of triethylamine is added to react for 20 hours in a nitrogen environment at 90 ℃, filtration is carried out after the reaction is finished, and the mixture is respectively washed clean with dry toluene and ethanol, and carbon octadeca chains can be embedded in the triazine covalent organic framework materials after the drying, so that the bromooctadecane and triazine covalent organic framework material modified silicon sphere novel stationary phase high performance liquid chromatography packing (Sil-COF-C18) is obtained.
Example 3
Preparing a novel stationary phase high performance liquid chromatography packing (Sil-COF-C18) of a silicon sphere modified by a bromooctadecane and triazine covalent organic framework material, wherein the high performance liquid chromatography packing is the novel stationary phase high performance liquid chromatography packing of the silicon sphere modified by the bromooctadecane and triazine covalent organic framework material, and specifically comprises the following steps:
(1) Weighing 5g of silicon spheres (particle size of 2-10 μm and pore diameter of ) Adding 150mL of 1mol/L HCl solution, stirring at 90 ℃ for reaction for 5 hours, filtering, washing with purified water to be neutral, and drying at 50-100 ℃ for 24 hours to obtain activated silicon spheres (Silica);
(2) Weighing 3g of the activated silicon spheres (Silica) prepared in the step (1), adding the activated silicon spheres into toluene for ultrasonic suspension, adding 1.89mL (8 mmol) of 3-aminopropyl triethoxysilane (APTES), carrying out ultrasonic treatment until the activated silicon spheres are uniformly dispersed, stirring and refluxing for 24 hours under the conditions of 100 ℃ and nitrogen protection, filtering and washing the activated silicon spheres with absolute ethyl alcohol after the reaction is finished, and carrying out vacuum drying for 2 hours at the normal temperature of 100 ℃ to obtain silicon spheres (Sil-APTES) bonded with a silanization reagent for later use;
(3) Weighing 0.5g of silicon spheres (Sil-APTES) bonded with the silanization reagent prepared in the step (2), placing in 30mL of 1, 4-dioxane, adding 41mg of 1,3, 5-benzene trialdehyde, 90.0mg of 1,3, 5-tris (4-aminophenyl) benzene triazine (TAPT), carrying out ultrasonic treatment until the mixture is uniformly dispersed, adding 1.6mL of acetic acid (AcOH) with the concentration of 12mol/L, stirring for 3 days in a room temperature environment, washing with ethanol after the reaction is finished to obtain a crude product, fully reducing the crude product with 50mL of 2% sodium hydrogen borate solution, and then carrying out vacuum drying at 60 ℃ for 24 hours to bond triazine covalent organic framework materials on the surfaces of the silicon spheres to obtain silicon spheres (Sil-COF) bonded with triazine covalent organic framework materials for standby;
(4) 3g of 1-bromooctadecane is immersed in 5ml of dry toluene to obtain a mixture II, 250ml of dry toluene is continuously added to fully dissolve the mixture II to obtain a mixture III, 3g of silicon spheres (Sil-COF) of which the surfaces are bonded with triazine covalent organic framework materials prepared in the step (3) are added, 2.55ml of triethylamine is added to react for 20 hours in a nitrogen environment of 100 ℃, filtration is carried out after the reaction is finished, and the mixture is respectively washed clean with dry toluene and ethanol, and carbon octadeca chains can be embedded in the triazine covalent organic framework materials after the drying, thus obtaining the novel stationary phase high performance liquid chromatography packing (Sil-COF-C18) of the silicon spheres of which the bromooctadecane and the triazine covalent organic framework materials are modified.
Physical property test
1. Elemental analysis was performed on the activated Silica spheres (Silica), the Silica spheres with triazine covalent organic framework material bonded to the surface (Sil-COF), and the novel stationary phase high performance liquid chromatography packing (Sil-COF-C18) modified with bromooctadecane and triazine covalent organic framework material prepared in example 1, and the results are shown in table 1. As can be seen from the elemental analysis results of Table 1, the functional groups containing C and N can be bonded to the activated silica spheres by the reaction in example 1, and silica spheres (Sil-COF) with the triazine covalent organic framework material bonded on the surfaces are prepared, and then novel stationary phase high performance liquid chromatography packing (Sil-COF-C18) with the bromooctadecane and triazine covalent organic framework material modified silica spheres is obtained.
TABLE 1 elemental analysis results for Silica, sil-COF and Sil-COF-C18
2. And respectively carrying out infrared spectrum scanning on each substance in the process of preparing the novel stationary phase high performance liquid chromatography packing (Sil-COF-C18) of the bromooctadecane and triazine covalent organic framework material modified silicon spheres in the embodiment 1 to obtain an infrared spectrum as shown in figure 1, wherein a is the novel stationary phase high performance liquid chromatography packing (Sil-COF-C18) of the bromooctadecane and triazine covalent organic framework material modified silicon spheres (Sil-COF) of which the surfaces are bonded with spherical covalent organic framework materials, and C is the silicon spheres (Sil-APTES) of which the surface is bonded with a silanization reagent. According to characteristic peaks such as 2937cm -1、2865cm-1、1664cm-1、1516cm-1 on a Sil-COF-C18 infrared spectrum line in the figure 1, the preparation method can be used for bonding a carbon-octadeca-and triazine covalent organic framework material on a silicon sphere to obtain a novel stationary phase high performance liquid chromatography packing (Sil-COF-C18) of the silicon sphere modified by the target products bromooctadeca-and triazine covalent organic framework material.
3. And further carrying out thermogravimetric analysis on each substance in the process of preparing the bromooctadecane and triazine covalent organic framework material modified silicon sphere novel stationary phase high performance liquid chromatography packing (Sil-COF-C18) in the embodiment 1, wherein the obtained spectrogram is shown in figure 2, a is activated silicon sphere (Silica), and b is bromooctadecane and triazine covalent organic framework material modified silicon sphere novel stationary phase high performance liquid chromatography packing (Sil-COF-C18). From fig. 2, it can be further proved that the preparation method of the invention can successfully bond the carbon octadecanoic chain and triazine covalent organic framework material on the silicon spheres to obtain the target products bromooctadecanoic alkane and triazine covalent organic framework material modified silicon sphere novel stationary phase high performance liquid chromatography packing (Sil-COF-C18).
Also, the above-mentioned test was performed on the obtained products prepared in example 2 and example 3, and the results obtained were similar to the physical properties of the products in example 1, indicating that it was possible to prepare a novel stationary phase high performance liquid chromatography packing (Sil-COF-C18) of silicon spheres modified with bromooctadecane and triazine covalent organic framework materials by the method of the present invention.
Chromatographic performance evaluation of high performance liquid chromatography packing
The high performance liquid chromatography packing (Sil-COF-C18) prepared in example 1 was prepared by a high pressure homogenization method, and the specification of the high performance liquid chromatography column was 4.6mm in inner diameter and 150mm in column length, and was used for the following retention mechanism test, specifically as follows:
When the retention mechanism of polycyclic aromatic hydrocarbon substances on the stationary phase is examined: the chromatogram obtained by selecting acetonitrile/water as mobile phase, flow rate of 1.0mL/min, detection wavelength of 254nm, column temperature of 30deg.C, and separating polycyclic aromatic hydrocarbon substances is shown in figure 3, wherein the polycyclic aromatic hydrocarbon substances corresponding to retention time at 1,2, 3 and 4 are naphthalene, fluorene, phenanthrene and fluoranthene respectively. As can be seen from fig. 3, the retention times generated by different polycyclic aromatic hydrocarbon species are not the same. It can be seen that the high performance liquid chromatography packing (Sil-COF-C18) prepared in example 1 was able to detect and separate different polycyclic aromatic hydrocarbon compounds when used as a stationary phase.
When examining the retention mechanism of alkylbenzene species on the stationary phase: the chromatogram obtained by selecting acetonitrile/water as mobile phase, flow rate of 1.0mL/min, detection wavelength of 214nm, column temperature of 30deg.C, and separating alkylbenzene substances is shown in figure 4, wherein the polycyclic aromatic hydrocarbon substances corresponding to retention time at 1,2, 3, 4 and 5 are toluene, ethylbenzene, propylbenzene, butylbenzene and pentylene respectively. According to the difference of delay times of different alkylbenzenes in FIG. 4, it was confirmed that the high performance liquid chromatography packing (Sil-COF-C18) prepared in example 1 was able to detect and separate alkylbenzenes when used as a stationary phase.
When looking at the retention mechanism of the positional isomer species on the stationary phase: the chromatogram obtained by selecting acetonitrile/water as mobile phase, flow rate of 1.0mL/min, detection wavelength of 214nm, column temperature of 30deg.C, and separating positional isomer substances is shown in figure 5, wherein the polycyclic aromatic hydrocarbon substances corresponding to 1, 2 and 3 positions of retention time are p-terphenyl, o-terphenyl and triphenylene respectively. According to the difference of delay times of different positional isomer compounds in fig. 5, it was demonstrated that the high performance liquid chromatography packing (Sil-COF-C18) prepared in example 1 was able to detect and separate different positional isomer compounds when used as a stationary phase.
When examining the retention mechanism of anilines on the stationary phase: the chromatogram obtained by selecting acetonitrile/water as mobile phase, flow rate of 1.0mL/min, detection wavelength of 214nm, column temperature of 30deg.C, and separating aniline substances is shown in figure 6, wherein the polycyclic aromatic hydrocarbon substances corresponding to retention time at 1,2,3, 4 and 5 are respectively 1, 2-phenylenediamine, aniline, benzidine and 1-naphthylamine. According to the difference of delay times of different positional isomer compounds in fig. 6, it was demonstrated that the high performance liquid chromatography packing (Sil-COF-C18) prepared in example 1 was able to detect and separate different aniline compounds when used as stationary phase.
Also, the high performance liquid chromatography packing prepared in the above examples 2 and 3 was used for the high performance liquid chromatography packing prepared in the above example 1, and the separation effect on polycyclic aromatic hydrocarbon substances, alkylbenzene substances, isomer substances, aniline substances was similar to that of example 1, demonstrating that the high performance liquid chromatography packing prepared by the present invention has a good application prospect as a stationary phase in high performance liquid chromatography reversed phase separation.
In summary, the invention discloses a novel stationary phase high performance liquid chromatography packing of triazine covalent organic framework modified silica spheres, which is prepared by a method of bonding triazine covalent organic framework materials on the surfaces of silica spheres bonded with silanization reagents and embedding carbon-eighteen chains on the triazine covalent organic frameworks, and comprises the silica spheres bonded with silanization reagents, the triazine covalent organic framework materials bonded with the surfaces of the silica spheres bonded with silanization reagents and the high performance liquid chromatography packing of the carbon-eighteen chains embedded on the triazine covalent organic frameworks. The high performance liquid chromatography packing of the invention has excellent physical structures such as high mechanical strength, good physical and chemical properties and the like of silica gel packing, so that the packing can be applied in a reverse phase separation mode, and has the advantages of high separation speed, high separation selectivity and the like.
Finally, it is noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the present invention, which is intended to be covered by the claims of the present invention.
Claims (9)
1. The triazine covalent organic framework modified silica sphere novel stationary phase high performance liquid chromatography packing is characterized by comprising silica spheres bonded with a silanization reagent, a covalent organic framework material bonded with the surface of the silica spheres bonded with the silanization reagent and an embedded carbon eighteen chain on the covalent organic framework material;
The covalent organic framework material is an amino bonding material obtained by reacting triazine covalent organic framework, 1,3, 5-benzene trialdehyde and a silanization reagent through Schiff base.
2. The method for preparing the high performance liquid chromatography packing according to claim 1, wherein the method comprises the following steps:
(1) Silicon sphere surface modification initiator: activating the porous silicon spheres by using acid to obtain activated silicon spheres, and then carrying out amination treatment on the surfaces of the silicon spheres by using a silylation reagent to obtain silicon spheres bonded with the silylation reagent;
(2) And bonding triazine covalent organic framework materials on the surface of the silicon sphere bonded with the silanization reagent: carrying out Schiff base reaction on 1,3, 5-tris (4-aminophenyl) benzene triazine and 1,3, 5-benzene trialdehyde and the silicon spheres bonded with the silylation agent obtained in the step (1) to generate an amino bonding material, namely bonding a covalent organic framework material on the surfaces of the silicon spheres bonded with the silylation agent;
(3) Embedding carbon eighteen chains on the triazine covalent organic framework material: and (3) carrying out chemical reaction on bromooctadecane and the silicon spheres with the surface bonded with the triazine covalent organic framework material obtained in the step (2), and embedding carbon octadeca chains on the covalent organic framework material to obtain the Schiff base covalent organic framework modified silicon spheres novel stationary phase high performance liquid chromatography packing.
3. The method according to claim 2, wherein in the step (1), the porous silicon spheres have a particle diameter of 2 to 10 μm and a pore diameter of
4. The preparation method according to claim 2, wherein in the step (1), the specific method of the amination treatment is as follows: firstly, ultrasonically suspending the activated silicon spheres by toluene, adding a silanization reagent, reacting for 3-24 hours at the temperature of 100-120 ℃ under the protection of nitrogen, filtering and cleaning by absolute ethyl alcohol after the reaction is finished, and vacuum drying for 5-24 hours at normal temperature or for 2-10 hours at 50-100 ℃ to obtain the silicon spheres bonded with the silanization reagent;
the silylating agent is 3-aminopropyl triethoxysilane;
The mass molar ratio of the activated silicon spheres to the silanization reagent is 1.5-3:8-15, g: mmol;
The activated silicon spheres are prepared according to the following method: adding the silicon spheres into hydrochloric acid solution with the concentration of 1mol/L according to the mass-volume ratio of 1:30 and g/mL, stirring for 3-5h at 90-100 ℃, filtering, washing with water to be neutral, and drying for 5-24 h at 50-100 ℃ to obtain the activated silicon spheres.
5. The preparation method according to claim 2, wherein in the step (2), the method for bonding triazine covalent organic framework material to the surface of the silicon sphere bonded with the silylating agent specifically comprises the following steps: adding an organic solvent into the silicon spheres bonded with the silylation agent prepared in the step (1) for dissolving to obtain a mixture I, then continuously adding 1,3, 5-tris (4-aminophenyl) benzene triazine and 1,3, 5-benzene trialdehyde to fully dissolve to obtain a mixed solution, adding an acetic acid solution, carrying out Schiff base reaction for 3-4 days in the environment of 120 ℃, filtering after the reaction is finished, washing with ethanol to obtain a crude product, fully reducing the crude product with a sodium hydrogen borate solution, and bonding triazine covalent organic framework materials on the surfaces of the silicon spheres bonded with the silylation agent after drying.
6. The preparation method according to claim 5, wherein the mass ratio of the silicon spheres bonded with the silylating agent, the 1,3, 5-tris (4-aminophenyl) benzene triazine and the 1,3, 5-benzene trialdehyde is 0.5:90 to 91:40 to 41;
the organic solvent is 1, 4-dioxane;
The mass volume ratio of the silicon spheres bonded with the silanization reagent to the organic solvent is 1:50-60, g: mL;
The concentration of the acetic acid solution is 12mol/L, and the volume ratio of the acetic acid to the mixed solution is 1:12-15;
the concentration of the sodium hydrogen borate solution is 2%;
The mass volume ratio of the crude product to the sodium hydrogen borate solution is 1:20-25, g is mL;
The drying is normal temperature vacuum drying or vacuum drying for 10-24 h at 50-100 ℃.
7. The method according to claim 2, wherein in the step (3), the method for embedding the carbon-octadecanoic chain on the triazine covalent organic framework material is specifically as follows: immersing 1-bromooctadecane in dry toluene according to the mass-volume ratio of 2-3:5-6 and g/ml to obtain a mixture II according to the following weight-volume ratio of 1: adding dry toluene to make it fully dissolved to obtain mixture III, adding the product prepared in step (2), adding triethylamine, making reaction for 20-24 hr under nitrogen atmosphere at 90-100 deg.C, filtering after reaction, respectively using dry toluene and ethyl alcohol to wash them clean, drying so as to obtain the invented product.
8. The process according to claim 7, wherein the mass ratio of the 1-bromooctadecane to the product produced in the step (2) is 1:1, a step of;
the volume ratio of triethylamine to dry toluene added to mixture III was 1:99 to 100;
The drying is normal temperature vacuum drying or vacuum drying for 10-24 h at 50-100 ℃.
9. The application of the high performance liquid chromatography packing as a stationary phase in high performance liquid chromatography reversed phase separation, wherein the compound type separated in the reversed phase separation is any one of alkylbenzene compounds, positional isomer compounds, aniline compounds or polycyclic aromatic hydrocarbon compounds containing different numbers of carbon atom alkyl chain substitution.
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Inventor after: Wang Lujun Inventor after: Ou Jing Inventor after: Yang Yaxin Inventor after: Dai Xuemei Inventor after: Wan Meijun Inventor after: Zhou Jingqiu Inventor after: Erguluhong Inventor before: Ou Jing Inventor before: Yang Yaxin Inventor before: Dai Xuemei Inventor before: Wan Meijun Inventor before: Zhou Jingqiu Inventor before: Erguluhong |
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