CN110876925A - Mixed-mode chromatographic stationary phase and preparation method and application thereof - Google Patents
Mixed-mode chromatographic stationary phase and preparation method and application thereof Download PDFInfo
- Publication number
- CN110876925A CN110876925A CN201811032390.5A CN201811032390A CN110876925A CN 110876925 A CN110876925 A CN 110876925A CN 201811032390 A CN201811032390 A CN 201811032390A CN 110876925 A CN110876925 A CN 110876925A
- Authority
- CN
- China
- Prior art keywords
- stationary phase
- sio
- compounds
- mixed
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 230000005526 G1 to G0 transition Effects 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 43
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 43
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 43
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 43
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims abstract description 9
- 150000004996 alkyl benzenes Chemical class 0.000 claims abstract description 8
- 239000000741 silica gel Substances 0.000 claims abstract description 8
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 8
- 150000007513 acids Chemical class 0.000 claims abstract description 7
- 230000007935 neutral effect Effects 0.000 claims abstract description 6
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims abstract description 6
- -1 acidic compounds Chemical class 0.000 claims abstract description 4
- 239000004005 microsphere Substances 0.000 claims abstract description 4
- 238000007740 vapor deposition Methods 0.000 claims abstract description 3
- 238000004811 liquid chromatography Methods 0.000 claims description 10
- 150000007514 bases Chemical class 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 238000010898 silica gel chromatography Methods 0.000 claims description 2
- FRIKWZARTBPWBN-UHFFFAOYSA-N [Si].O=[Si]=O Chemical compound [Si].O=[Si]=O FRIKWZARTBPWBN-UHFFFAOYSA-N 0.000 claims 2
- 238000000151 deposition Methods 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract 2
- 239000012071 phase Substances 0.000 description 24
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- 238000000926 separation method Methods 0.000 description 15
- 230000014759 maintenance of location Effects 0.000 description 13
- 239000000377 silicon dioxide Substances 0.000 description 13
- 238000013375 chromatographic separation Methods 0.000 description 12
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthene Chemical compound C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 10
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 10
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 8
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 8
- 239000007853 buffer solution Substances 0.000 description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 8
- 238000001514 detection method Methods 0.000 description 7
- 238000004587 chromatography analysis Methods 0.000 description 6
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 5
- QZYHIOPPLUPUJF-UHFFFAOYSA-N 3-nitrotoluene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1 QZYHIOPPLUPUJF-UHFFFAOYSA-N 0.000 description 5
- 238000002013 hydrophilic interaction chromatography Methods 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 230000003993 interaction Effects 0.000 description 5
- JLIDBLDQVAYHNE-YKALOCIXSA-N (+)-Abscisic acid Chemical compound OC(=O)/C=C(/C)\C=C\[C@@]1(O)C(C)=CC(=O)CC1(C)C JLIDBLDQVAYHNE-YKALOCIXSA-N 0.000 description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 238000004255 ion exchange chromatography Methods 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachlorophenol Chemical compound OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004190 ion pair chromatography Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- 238000004366 reverse phase liquid chromatography Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- WSEQXVZVJXJVFP-HXUWFJFHSA-N (R)-citalopram Chemical compound C1([C@@]2(C3=CC=C(C=C3CO2)C#N)CCCN(C)C)=CC=C(F)C=C1 WSEQXVZVJXJVFP-HXUWFJFHSA-N 0.000 description 2
- PRPINYUDVPFIRX-UHFFFAOYSA-N 1-naphthaleneacetic acid Chemical compound C1=CC=C2C(CC(=O)O)=CC=CC2=C1 PRPINYUDVPFIRX-UHFFFAOYSA-N 0.000 description 2
- VGVRPFIJEJYOFN-UHFFFAOYSA-N 2,3,4,6-tetrachlorophenol Chemical class OC1=C(Cl)C=C(Cl)C(Cl)=C1Cl VGVRPFIJEJYOFN-UHFFFAOYSA-N 0.000 description 2
- HSQFVBWFPBKHEB-UHFFFAOYSA-N 2,3,4-trichlorophenol Chemical compound OC1=CC=C(Cl)C(Cl)=C1Cl HSQFVBWFPBKHEB-UHFFFAOYSA-N 0.000 description 2
- UMPSXRYVXUPCOS-UHFFFAOYSA-N 2,3-dichlorophenol Chemical compound OC1=CC=CC(Cl)=C1Cl UMPSXRYVXUPCOS-UHFFFAOYSA-N 0.000 description 2
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 2
- 241000208140 Acer Species 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229960001653 citalopram Drugs 0.000 description 2
- FCRACOPGPMPSHN-UHFFFAOYSA-N desoxyabscisic acid Natural products OC(=O)C=C(C)C=CC1C(C)=CC(=O)CC1(C)C FCRACOPGPMPSHN-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- JTEDVYBZBROSJT-UHFFFAOYSA-N indole-3-butyric acid Chemical compound C1=CC=C2C(CCCC(=O)O)=CNC2=C1 JTEDVYBZBROSJT-UHFFFAOYSA-N 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- VGKDLMBJGBXTGI-SJCJKPOMSA-N sertraline Chemical compound C1([C@@H]2CC[C@@H](C3=CC=CC=C32)NC)=CC=C(Cl)C(Cl)=C1 VGKDLMBJGBXTGI-SJCJKPOMSA-N 0.000 description 2
- 229960002073 sertraline Drugs 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XWTYSIMOBUGWOL-UHFFFAOYSA-N (+-)-Terbutaline Chemical compound CC(C)(C)NCC(O)C1=CC(O)=CC(O)=C1 XWTYSIMOBUGWOL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- NDAUXUAQIAJITI-UHFFFAOYSA-N albuterol Chemical compound CC(C)(C)NCC(O)C1=CC=C(O)C(CO)=C1 NDAUXUAQIAJITI-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000002009 diols Chemical group 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000003147 glycosyl group Chemical group 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012434 mixed-mode chromatography Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229960002052 salbutamol Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229960000195 terbutaline Drugs 0.000 description 1
- 238000000825 ultraviolet detection Methods 0.000 description 1
Images
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
- B01J20/282—Porous sorbents
- B01J20/283—Porous sorbents based on silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
- B01D15/265—Adsorption 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a mixed-mode chromatographic stationary phase and a preparation method and application thereof. The stationary phase g-C3N4@SiO2Depositing g-C on the surface of silica gel microspheres by vapor deposition3N4Post-preparation simple and cheap liquid chromatogram stationary phase g-C3N4@SiO2. The liquid chromatogram stationary phase is filled in a chromatographic column to effectively separate electron donor acceptor compounds such as acidic compounds, neutral polar compounds, alkaline compounds, alkylbenzene, polycyclic aromatic hydrocarbon or nitrobenzene and the like. Stationary phase g-C of the invention3N4@SiO2The preparation is simple, the reproducibility is good, and the application prospect is good.
Description
Technical Field
The invention relates to a chromatographic stationary phase material, in particular to a mixed-mode chromatographic stationary phase, and also relates to a preparation method and application of the chromatographic stationary phase.
Background
With the recent years, proteomics, metabonomics, genomics, agriculture, food chemistry and environmentWith the rapid development of chemistry, pharmaceutical chemistry, and the like, the separation and analysis of various compounds in a complex sample is becoming an increasingly important issue. Among them, the reverse phase chromatographic separation mode based on the principle of hydrophobic interaction separation is currently the most widely used one, but those compounds having a stronger polarity or having ionic groups are used in C8Or C18It is difficult to retain and separate on conventional reversed phase chromatography (RPLC) stationary phases such as bonded silica gel; the application of the traditional normal phase chromatography is limited by the problems of poor solubility of polar analytes in a mobile phase, incompatibility of a nonpolar mobile phase and a mass spectrum, great environmental pollution of an organic solvent and the like; hydrophilic interaction chromatography (HILIC) adopts a polar stationary phase used in a normal phase chromatography mode, a polar mobile phase of reversed phase chromatography is used for separating strong polarity and charged micromolecule compounds, the HILIC has the advantages of good solubility of a polar sample in the mobile phase, good compatibility with Mass Spectrum (MS) and the like, and becomes one of choices in the chromatography separation mode, at present, various stationary phases are applied to the HILIC, such as chromatographic stationary phases of naked silica gel and modified silica gel of amino, diol group, glycosyl and the like, however, although the hydrophilic interaction chromatography is developed and improved for years, the separation selectivity of the stationary phase is insufficient, the solubility of the mobile phase with high organic phase content limits the sample, and the complex compounds cannot be separated well; ion Exchange Chromatography (IEC) and Ion Pair Chromatography (IPC) can also effectively solve the separation problem of part of ionic compounds, but IEC has low selectivity when separating some polypeptide compounds with the same charge, and IEC and IPC are not compatible with mass spectrum (ESI-MS) due to the existence of high-concentration salt and ion pair reagent which is difficult to volatilize. For the increasingly complex separation of compounds from matrix samples, a single chromatography mode based on one retention is difficult to meet, and Mixed Mode (MMC) chromatography modes based on two or more retention are beginning to attract increasing attention from scholars.
Mixed Mode (MMC) chromatography mode was first proposed by Brown et al in 1986, where various functional groups are present on the surface of the MMC's stationary phase, which can produce various interactions with solutes to be separated. The MMC is used as a substitute or complementary separation mode of the traditional chromatogram, can provide a plurality of retention mechanisms to improve the separation selectivity, can also improve the problem of tailing of basic compounds in reversed phase chromatogram, can easily adjust the condition of a mobile phase to realize better separation, has the characteristics of good compatibility with ESI-MS and the like, and has better separation effect on the simultaneous separation of charged, polar, nonpolar and other compounds.
g-C3N4As a two-dimensional lamellar material without metal polymer, the material has the advantages of higher stability, good biocompatibility, controllable energy band structure, no toxicity and the like, and is widely applied in various research fields. g-C3N4The surface has hydrophobicity, pi-pi electrons and negative charge, contains various functional groups, but g-C3N4Have not been used in the field of chromatographic separations.
The silica gel has the characteristics of silicon hydroxyl group with a surface for modification, controllable specific surface and pore structure, and is most widely used as a chromatographic stationary phase matrix. When the silica is used as a stationary phase to separate alkaline compounds, the phenomena of tailing, serious peak broadening and the like easily occur in the peak shape.
Disclosure of Invention
The present invention aims to overcome the above-mentioned disadvantages and to provide a mixed-mode liquid chromatography stationary phase which is typically a mixed-mode chromatography stationary phase having hydrophilic, hydrophobic, ion-exchange and charge-transfer properties. The second purpose of the invention is to provide a preparation method of the mixed-mode liquid chromatography stationary phase, which adopts a gas phase deposition method to deposit g-C on the surface of silica gel microspheres3N4Post-preparation of a simple and inexpensive g-C3N4@SiO2A liquid chromatography stationary phase. The invention also aims to provide the use of the mixed mode liquid chromatography stationary phase.
In order to achieve the purpose, the invention adopts the following technical scheme:
mixed-mode liquid chromatography stationary phase g-C3N4@SiO2The structure is as follows:
in one aspect, the mixed mode liquid chromatography stationary phase g-C described above is provided3N4@SiO2The preparation method comprises depositing g-C on the surface of silica gel microspheres by vapor deposition3N4The method comprises the following specific steps: melamine and silicon dioxide spheres are mixed according to the weight ratio of 1: 1, uniformly mixing, transferring into a crucible, heating to 550 ℃ at the speed of 5 ℃/min in a muffle furnace, and keeping for 1h to obtain C3N4Precipitated silica gel chromatography stationary phase g-C3N4@SiO2(ii) a The specific surface of the silicon dioxide spheres is 250m2The pore diameter is 10nm, and the reaction formula is as follows:
in another aspect, there is provided the mixed mode liquid chromatography stationary phase g-C described above3N4@SiO2The application in separating electron donor acceptor compounds such as acidic compounds, neutral polar compounds, basic compounds, alkylbenzene, polycyclic aromatic hydrocarbon or nitrobenzene and the like.
The invention has the positive effects that:
(1) mixed mode liquid phase chromatographic stationary phase g-C3N4@SiO2The presence of hydrophilic, hydrophobic, ion exchange and charge transfer interactions is a typical mixed mode chromatographic stationary phase.
(2) Mixed mode liquid phase chromatographic stationary phase g-C3N4@SiO2Can be used for separating various compounds such as acidic compounds, neutral polar compounds, basic compounds and the like.
Drawings
FIG. 1 is a diagram of the mechanism of hydrophobic interaction of the stationary phase.
(A) The graph is a plot of retention factor log for alkylbenzene versus the number of methylene groups for alkylbenzene; (B) the figure is a graph of the logarithm of the retention factor of the polycyclic aromatic hydrocarbon and the change of the content of the acetonitrile in the mobile phase.
FIG. 2 shows acidic and basic compoundsIs in g-C3N4@SiO2With SiO2Chromatogram on stationary phase.
FIG. 3 shows the neutral compound in g-C3N4@SiO2With SiO2Chromatogram on stationary phase. (A) Peak of chromatogram: 1. biphenyl; 2. (ii) acrylamide; 3. dimethyl sulfoxide maple; 4. and (3) thiourea. (B) Peak of the chromatogram: 1. naphthalene; fluorene; 3. phenanthrene; 4. and (3) fluoranthene.
FIG. 4 shows chlorophenols in g-C3N4@SiO2With SiO2Chromatogram on stationary phase.
FIG. 5 shows the reaction of m-dinitrobenzene and m-nitrotoluene in (A) g-C3N4@SiO2With SiO2And (B) C18-SiO2Chromatogram on stationary phase.
Detailed Description
The features and advantages of the present invention will be further understood from the following detailed description taken in conjunction with the accompanying drawings. The examples provided are merely illustrative of the method of the present invention and do not limit the remainder of the disclosure in any way.
Example 1:
g to C3N4@SiO2Loading into a 150mm × 4.6mm (i.d.) chromatographic column, examining the retention of 4 alkylbenzenes such as benzene, toluene, ethylbenzene, propylbenzene and 4 polycyclic aromatic hydrocarbons (fluorene, phenanthrene, anthracene, and fluoranthene) on the column, and examining the retention of alkylbenzenes in g-C3N4@SiO2The relationship between the logarithm of retention factor on the stationary phase and the number of methylene groups of alkylbenzene, as shown in FIG. 1(A), at g-C3N4@SiO2The retention on the column is gradually enhanced along with the increase of the number of methylene groups, and a better linear relation is presented; 4 Polycyclic Aromatic Hydrocarbons (PAHs) in g-C were also investigated3N4@SiO2The relationship between the logarithm of retention factors on the stationary phase and the acetonitrile content in the mobile phase, as shown in FIG. 1B, 4 PAHs at g-C3N4@SiO2On-column retention enhanced with increasing acetonitrile content in the mobile phase by plotting the logarithm of the polycyclic aromatic hydrocarbon retention factor against the change in acetonitrile content in the mobile phase ((FIG. 1: (C.))B) ) it can be seen that the logk varies with acetonitrile content in good linearity. These all represent g-C3N4@SiO2The hydrophobic interaction retention mechanism of chromatographic stationary phases.
Mobile phase of fig. 1 (a): ACN/H2O (10/90, v/v); mobile phase of fig. 1 (B): ACN/20mM HCOONH4(pH 6.0) buffer solution.
The flow rate is 1.0 mL/min; ultraviolet detection wavelength: 254 nm; the column temperature is 40 ℃; the injection volume is 10 muL.
Example 2:
g to C3N4@SiO2With SiO2Loading the mixture into a chromatographic column of 150mm × 4.6mm (i.d.), respectively, and then comparing the mixture with the chromatographic separation of 4 acidic compounds (indolebutyric acid, abscisic acid, naphthylacetic acid, benzoic acid) and 4 basic compounds (sertraline, citalopram, m-hydroxy-tert-buterelin, hydroxymethyl-tert-buterelin), wherein the 4 acidic compounds and the 4 basic compounds are in g-C3N4@SiO2Good separation was obtained on the stationary phase (FIG. 2).
Figure (a) chromatographic separation of acidic compounds: mobile phase: ACN/20mM HCOONH4(pH 6.0) buffer solution (90/10, v/v); the flow rate is 1.0 mL/min; the column temperature is 40 ℃; the sample injection volume is 10 mu L; the detection wavelength is 230 nm. Chromatographic peak: 1. indolebutyric acid; 2. abscisic acid; 3. naphthylacetic acid; 4. benzoic acid.
Figure (B) chromatographic separation of basic compounds: mobile phase: ACN/20mM HCOONH4(pH 6.0) buffer solution (88/12, v/v); the flow rate is 1.0 mL/min; the column temperature is 40 ℃; the sample injection volume is 10 mu L; the detection wavelength is 240 nm. Chromatographic peak: 1. sertraline; 2. citalopram; 3. terbutaline; 4. salbutamol.
Example 3:
g to C3N4@SiO2With SiO2Are respectively filled in chromatographic columns of 150mm multiplied by 4.6mm (i.d.), and then used for the chromatographic separation comparison of 4 neutral compounds (biphenyl, acrylamide, dimethyl sulfoxide, thiourea) and 4 condensed ring aromatic hydrocarbons (naphthalene, fluorene, phenanthrene, fluoranthene) in g-C3N4@SiO2On the stationary phase to obtainA better separation effect is achieved (fig. 3).
FIG. A shows the chromatographic separation of a mixture of biphenyl, acrylamide, dimethylsulfoxide and thiourea.
Mobile phase: ACN/20mM HCOONH4(pH 6.0) buffer solution (96/4, v/v); the flow rate is 1.0 mL/min; the column temperature is 40 ℃; the sample injection volume is 10 mu L; the detection wavelength is 254 nm. Chromatographic peak: 1. biphenyl; 2. an acrylamide; 3. dimethyl sulfoxide maple; 4. and (3) thiourea.
In the diagram (B), the chromatographic separation of the mixture of naphthalene, fluorene, phenanthrene and fluoranthene is carried out.
Mobile phase: ACN/20mM HCOONH4(pH 6.0) buffer solution (40/60, v/v); the flow rate is 1.0 mL/min; the column temperature is 40 ℃; the sample injection volume is 10 mu L; the detection wavelength is 240 nm. Chromatographic peak: 1. naphthalene; 2. fluorene; 3. phenanthrene; fluoranthene.
Example 4:
g to C3N4@SiO2With SiO2Loading into 150mm × 4.6mm (i.d.) chromatographic columns, respectively, and comparing the chromatographic separation of 4 chlorophenols (chlorophenol, dichlorophenol, trichlorophenol, and pentachlorophenol) in g-C3N4@SiO2Better separation was obtained on the stationary phase (fig. 4).
Chromatographic conditions are as follows: the solvent A is 20mM HCOONH4(pH 6.0) buffer solution, and solvent B is ACN solution. The mobile phase gradient program is (t represents time (min)): t is t0,20％B；t1090% B; the flow rate is 1.0 mL/min; the column temperature is 40 ℃; the sample injection volume is 10 mu L; the detection wavelength is 240 nm. Chromatographic peak: 1. chlorophenol; dichlorophenol; 3. trichlorophenol; 4. pentachlorophenol.
Example 5:
g to C3N4@SiO2、SiO2And octadecyl bonded silica gel (ODS) were packed in a column of 150 mm. times.4.6 mm (i.d.), respectively, and then used for the chromatographic separation of m-dinitrobenzene and m-nitrotoluene, which were compared in g-C3N4@SiO2The stationary phase gave a better separation (FIG. 5), which was retained in the opposite order to the ODS column, showing a typical chargeThe mechanism of transfer.
In the figure (A), m-dinitrobenzene and m-nitrotoluene are present in g-C3N4@SiO2、SiO2Chromatographic separation on stationary phase. Mobile phase: ACN/20mM HCOONH4(pH 6.0) buffer solution (20/80, v/v); the flow rate is 1.0 mL/min; the column temperature is 40 ℃; the sample injection volume is 10 mu L; the detection wavelength is 240 nm. .
In FIG. B, the chromatographic separation of m-dinitrobenzene and m-nitrotoluene on an ODS stationary phase is carried out.
Mobile phase: ACN/20mM HCOONH4(pH 6.0) buffer solution (80/20, v/v); the flow rate is 1.0 mL/min; the column temperature is 40 ℃; the sample injection volume is 10 mu L; the detection wavelength is 240 nm.
Chromatographic peak: m-dinitrobenzene; 2. m-nitrotoluene.
Claims (3)
1. Mixed-mode liquid chromatography stationary phase g-C3N4@SiO2The structure is characterized in that:
2. the mixed mode liquid chromatography stationary phase g-C of claim 13N4@SiO2The preparation method is characterized in that g-C is deposited on the surface of the silica gel microsphere by adopting a vapor deposition method3N4The method comprises the following specific steps: melamine and silicon dioxide silicon spheres are mixed according to the weight ratio of 1: 1, uniformly mixing, transferring into a crucible, heating to 550 ℃ at the speed of 5 ℃/min in a muffle furnace, and keeping for 1h to obtain C3N4Precipitated silica gel chromatography stationary phase g-C3N4@SiO2(ii) a The specific surface of the silicon dioxide silicon spheres is 250m2The pore diameter is 10nm, and the reaction formula is as follows:
3. the mixed mode liquid chromatography stationary phase g-C of claim 13N4@SiO2The application in separating electron donor acceptor compounds such as acidic compounds, neutral polar compounds, basic compounds, alkylbenzene, polycyclic aromatic hydrocarbon or nitrobenzene and the like.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811032390.5A CN110876925B (en) | 2018-09-05 | 2018-09-05 | Mixed-mode chromatographic stationary phase and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811032390.5A CN110876925B (en) | 2018-09-05 | 2018-09-05 | Mixed-mode chromatographic stationary phase and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110876925A true CN110876925A (en) | 2020-03-13 |
| CN110876925B CN110876925B (en) | 2022-04-12 |
Family
ID=69726901
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811032390.5A Expired - Fee Related CN110876925B (en) | 2018-09-05 | 2018-09-05 | Mixed-mode chromatographic stationary phase and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110876925B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114471450A (en) * | 2022-02-15 | 2022-05-13 | 华北理工大学 | g-C3N4@SiO2Preparation method of (1) |
| CN115554998A (en) * | 2022-09-30 | 2023-01-03 | 淮阴工学院 | Synthetic method of naphthalene-embedded mixed ligand-modified alkyl stationary phase |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1325847A (en) * | 2000-05-18 | 2001-12-12 | 国家淀粉及化学投资控股公司 | Compound with electron providing and receiving functional groups |
| CN103301822A (en) * | 2012-10-25 | 2013-09-18 | 中国人民解放军第四军医大学 | Polar liquid chromatogram filler and preparation method thereof |
| CN105921097A (en) * | 2016-06-01 | 2016-09-07 | 南京航空航天大学 | Preparation method and application of mesoporous graphite phase carbon nitride |
| CN107262076A (en) * | 2016-04-06 | 2017-10-20 | 中国科学院上海有机化学研究所 | A kind of hydrophilic interaction chromatographic stationary phases and preparation method thereof |
| CN108043375A (en) * | 2017-11-07 | 2018-05-18 | 南京赢点色谱分离技术有限公司 | A kind of preparation method of multi-mode combination vancomycin chromatographic stationary phases |
-
2018
- 2018-09-05 CN CN201811032390.5A patent/CN110876925B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1325847A (en) * | 2000-05-18 | 2001-12-12 | 国家淀粉及化学投资控股公司 | Compound with electron providing and receiving functional groups |
| CN103301822A (en) * | 2012-10-25 | 2013-09-18 | 中国人民解放军第四军医大学 | Polar liquid chromatogram filler and preparation method thereof |
| CN107262076A (en) * | 2016-04-06 | 2017-10-20 | 中国科学院上海有机化学研究所 | A kind of hydrophilic interaction chromatographic stationary phases and preparation method thereof |
| CN105921097A (en) * | 2016-06-01 | 2016-09-07 | 南京航空航天大学 | Preparation method and application of mesoporous graphite phase carbon nitride |
| CN108043375A (en) * | 2017-11-07 | 2018-05-18 | 南京赢点色谱分离技术有限公司 | A kind of preparation method of multi-mode combination vancomycin chromatographic stationary phases |
Non-Patent Citations (1)
| Title |
|---|
| QIANGBA GEZHEN等: ""Simple and Sensitive Determination of Aromatic Acids in Coconut Water by g-C3N4@SiO2 Based Solid-phase Extraction and HPLC-UV Analysis"", 《CHEM. RES. CHIN. UNIV》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114471450A (en) * | 2022-02-15 | 2022-05-13 | 华北理工大学 | g-C3N4@SiO2Preparation method of (1) |
| CN115554998A (en) * | 2022-09-30 | 2023-01-03 | 淮阴工学院 | Synthetic method of naphthalene-embedded mixed ligand-modified alkyl stationary phase |
| CN115554998B (en) * | 2022-09-30 | 2024-03-26 | 淮阴工学院 | Naphthalene-embedded mixed ligand modified alkyl stationary phase synthesis method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110876925B (en) | 2022-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Fumes et al. | Recent advances and future trends in new materials for sample preparation | |
| Yu et al. | Hydroxyfullerene as a novel coating for solid-phase microextraction fiber with sol–gel technology | |
| Yu et al. | Preparation of polydimethylsiloxane/β-cyclodextrin/divinylbenzene coated “dumbbell-shaped” stir bar and its application to the analysis of polycyclic aromatic hydrocarbons and polycyclic aromatic sulfur heterocycles compounds in lake water and soil by high performance liquid chromatography | |
| Zhao et al. | Determination of phenols in water using liquid phase microextraction with back extraction combined with high-performance liquid chromatography | |
| Bagheri et al. | Conductive polymers as new media for solid-phase extraction: Isolation of chlorophenols from water sample | |
| Wise et al. | Chemically-bonded aminosilane stationary phase for the high-performance liquid chromatographic separation of polynuclear aromatic compounds | |
| Li et al. | Evaluation of the solid-phase microextraction fiber coated with single walled carbon nanotubes for the determination of benzene, toluene, ethylbenzene, xylenes in aqueous samples | |
| Scott et al. | Examination of five commercially available liquid chromatographic reversed phases (including the nature of the solute-solvent-stationary phase interactions associated with them) | |
| Benedé et al. | Stir bar sorptive-dispersive microextraction mediated by magnetic nanoparticles–nylon 6 composite for the extraction of hydrophilic organic compounds in aqueous media | |
| Kozlík et al. | Effect of silica gel modification with cyclofructans on properties of hydrophilic interaction liquid chromatography stationary phases | |
| Li et al. | Determination of sulfonamide compounds in sewage and river by mixed hemimicelles solid-phase extraction prior to liquid chromatography–spectrophotometry | |
| CN110876925B (en) | Mixed-mode chromatographic stationary phase and preparation method and application thereof | |
| Chen et al. | Development of multiple monolithic fiber solid‐phase microextraction and liquid chromatography–tandem mass spectrometry method for the sensitive monitoring of aminoglycosides in honey and milk samples | |
| Hoai et al. | Simultaneous determination of degradation products of nonylphenol polyethoxylates and their halogenated derivatives by solid-phase extraction and gas chromatography–tandem mass spectrometry after trimethylsilylation | |
| Michel et al. | Porous graphitic carbon sorbents in biomedical and environmental applications | |
| Ji et al. | Diamond nanoparticles coating for in‐tube solid‐phase microextraction to detect polycyclic aromatic hydrocarbons | |
| Yang et al. | Magnetic porous aromatic framework with a core–shell structure as a sorbent for rapid extraction of phenols and their quantitation in urine by HPLC-UV | |
| Du et al. | Carbon molecular sieve based micro‐matrix‐solid‐phase dispersion for the extraction of polyphenols in pomegranate peel by UHPLC‐Q‐TOF/MS | |
| CN102221585A (en) | Application method of magnesium oxide microsphere in environmental water sample | |
| Li et al. | High performance liquid chromatography of aromatic carboxylic acids on p-tert-butyl-calix [8] arene-bonded silica gel stationary phase | |
| Suzuki et al. | Covalently bound ionene polyelectrolyte-silica gel stationary phases for HPLC | |
| Lee et al. | In-needle microextraction coupled with gas chromatography/mass spectrometry for the analysis of phthalates generating from food containers | |
| Rahimi et al. | Application of copolymer coated frits for solid-phase extraction of poly cyclic aromatic hydrocarbons in water samples | |
| Zhao et al. | Electrochromatographic performance of graphene and graphene oxide modified silica particles packed capillary columns | |
| Karlesky et al. | A study of polynuclear aromatic hydrocarbons on an amino bonded phase liquid chromatographic column in the normal and reversed phase |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20220412 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |