CN114984933A - Dendritic organic small molecule gel silicon-based stationary phase material based on benzyl ether and preparation method thereof - Google Patents
Dendritic organic small molecule gel silicon-based stationary phase material based on benzyl ether and preparation method thereof Download PDFInfo
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- CN114984933A CN114984933A CN202210720694.0A CN202210720694A CN114984933A CN 114984933 A CN114984933 A CN 114984933A CN 202210720694 A CN202210720694 A CN 202210720694A CN 114984933 A CN114984933 A CN 114984933A
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- tetrahydrofuran
- benzyl ether
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- gel
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- 238000002360 preparation method Methods 0.000 title claims abstract description 49
- 230000005526 G1 to G0 transition Effects 0.000 title claims abstract description 43
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000010703 silicon Substances 0.000 title claims abstract description 31
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 31
- 239000000463 material Substances 0.000 title claims abstract description 30
- 150000003384 small molecules Chemical class 0.000 title claims abstract description 28
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 239000000499 gel Substances 0.000 claims abstract description 64
- -1 amino silica gel Chemical compound 0.000 claims abstract description 39
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000000741 silica gel Substances 0.000 claims abstract description 18
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 18
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 claims abstract description 16
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 6
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 3
- 238000005576 amination reaction Methods 0.000 claims abstract description 3
- 239000011259 mixed solution Substances 0.000 claims description 155
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 142
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 71
- 238000003756 stirring Methods 0.000 claims description 54
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 238000001035 drying Methods 0.000 claims description 37
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- 239000007787 solid Substances 0.000 claims description 35
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 34
- 239000012265 solid product Substances 0.000 claims description 33
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 25
- 239000000725 suspension Substances 0.000 claims description 24
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 21
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 claims description 21
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 21
- DOSDTCPDBPRFHQ-UHFFFAOYSA-N dimethyl 5-hydroxybenzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC(O)=CC(C(=O)OC)=C1 DOSDTCPDBPRFHQ-UHFFFAOYSA-N 0.000 claims description 20
- 238000000605 extraction Methods 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 20
- 239000002244 precipitate Substances 0.000 claims description 20
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 18
- 238000010992 reflux Methods 0.000 claims description 14
- 239000002131 composite material Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000012044 organic layer Substances 0.000 claims description 12
- 238000004440 column chromatography Methods 0.000 claims description 10
- 239000000706 filtrate Substances 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 9
- 230000001376 precipitating effect Effects 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 6
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 5
- YWMLORGQOFONNT-UHFFFAOYSA-N [3-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC(CO)=C1 YWMLORGQOFONNT-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 238000002414 normal-phase solid-phase extraction Methods 0.000 abstract description 14
- 238000004128 high performance liquid chromatography Methods 0.000 abstract description 6
- 230000003993 interaction Effects 0.000 abstract description 6
- 239000000945 filler Substances 0.000 abstract description 4
- 239000012071 phase Substances 0.000 abstract description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 abstract description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 2
- 125000001033 ether group Chemical group 0.000 abstract description 2
- 125000003473 lipid group Chemical group 0.000 abstract description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 2
- 238000005342 ion exchange Methods 0.000 abstract 1
- 230000014759 maintenance of location Effects 0.000 abstract 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 18
- 238000000926 separation method Methods 0.000 description 10
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- 238000004366 reverse phase liquid chromatography Methods 0.000 description 8
- 238000013375 chromatographic separation Methods 0.000 description 6
- 238000009987 spinning Methods 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 239000005711 Benzoic acid Substances 0.000 description 4
- 235000010233 benzoic acid Nutrition 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000000265 homogenisation Methods 0.000 description 3
- 238000004255 ion exchange chromatography Methods 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 239000002777 nucleoside Substances 0.000 description 3
- 150000003833 nucleoside derivatives Chemical class 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- NYHBQMYGNKIUIF-UUOKFMHZSA-N Guanosine Chemical compound C1=NC=2C(=O)NC(N)=NC=2N1[C@@H]1O[C@H](CO)[C@@H](O)[C@H]1O NYHBQMYGNKIUIF-UUOKFMHZSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- OPTASPLRGRRNAP-UHFFFAOYSA-N cytosine Chemical compound NC=1C=CNC(=O)N=1 OPTASPLRGRRNAP-UHFFFAOYSA-N 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- RWQNBRDOKXIBIV-UHFFFAOYSA-N thymine Chemical compound CC1=CNC(=O)NC1=O RWQNBRDOKXIBIV-UHFFFAOYSA-N 0.000 description 2
- 229930024421 Adenine Natural products 0.000 description 1
- GFFGJBXGBJISGV-UHFFFAOYSA-N Adenine Chemical compound NC1=NC=NC2=C1N=CN2 GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 description 1
- MIKUYHXYGGJMLM-GIMIYPNGSA-N Crotonoside Natural products C1=NC2=C(N)NC(=O)N=C2N1[C@H]1O[C@@H](CO)[C@H](O)[C@@H]1O MIKUYHXYGGJMLM-GIMIYPNGSA-N 0.000 description 1
- NYHBQMYGNKIUIF-UHFFFAOYSA-N D-guanosine Natural products C1=2NC(N)=NC(=O)C=2N=CN1C1OC(CO)C(O)C1O NYHBQMYGNKIUIF-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 229930010555 Inosine Natural products 0.000 description 1
- UGQMRVRMYYASKQ-KQYNXXCUSA-N Inosine Chemical compound O[C@@H]1[C@H](O)[C@@H](CO)O[C@H]1N1C2=NC=NC(O)=C2N=C1 UGQMRVRMYYASKQ-KQYNXXCUSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 229960000643 adenine Drugs 0.000 description 1
- 229920013822 aminosilicone Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229940104302 cytosine Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000412 dendrimer Substances 0.000 description 1
- 229920000736 dendritic polymer Polymers 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 229940029575 guanosine Drugs 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229960003786 inosine Drugs 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 229920004010 poly(benzyl ether) Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000012056 semi-solid material Substances 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229940113082 thymine Drugs 0.000 description 1
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- 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
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- 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
- B01J20/286—Phases chemically bonded to a substrate, e.g. to silica or to polymers
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/08—Preparation using an enricher
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
- B01J2220/52—Sorbents specially adapted for preparative chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
- B01J2220/54—Sorbents specially adapted for analytical or investigative chromatography
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Abstract
Benzyl ether-based dendritic organic small molecule gel silicon-based stationary phase material prepared from SiO 2 Taking the amino silica gel as a carrier, carrying out amination reaction on the amino silica gel and cyanuric chloride, and then carrying out alkylation reaction on the amino silica gel and G3 to graft G3 on the surface of silicon dioxide to form SiO 2 -G3; the method also provides a preparation method of the dendritic organic small molecule gel silicon-based stationary phase material based on benzyl ether, which comprises the following steps: preparing 5-benzyl ether dimethyl isophthalate G1; preparation of G1-CH 2 OH; preparing dendritic organic small molecule gel G2; preparation of G2-CH 2 OH; preparing dendritic organic small molecule gel G3; preparation of SiO 2 ‑G3；SiO 2 G3 can be used as a novel mixed mode filler and a solid phase extraction filler of HPLC, integrates the advantages of silica microspheres and dendritic organic small molecule gel, overcomes the limitation of pure dendritic organic small molecule gel, and introduces hydrophilic triazine during grafting due to the coexistence of benzene ring, ether group, methyl group, lipid group and carbonyl group in G3, so that the stationary phase prepared by the method presents a hydrophilic interaction/reversed phase/ion exchange retention mechanism.
Description
The technical field is as follows:
the invention belongs to the field of preparation of solid-phase extraction fillers and high performance liquid chromatography fillers, and particularly relates to a preparation method of a dendritic organic small molecular gel silicon-based stationary phase material based on benzyl ether.
Background art:
solid phase extraction techniques and High Performance Liquid Chromatography (HPLC) techniques have been widely used in qualitative and quantitative analysis in various fields. The stationary phase is of great interest as the core of solid phase extraction and HPLC systems. Various mixed mode stationary phases, such as hydrophilic chromatography (HILIC)/reverse phase chromatography (RPL), RPLC/ion chromatography (IEC), HILIC/IEC and HILIC/RPLC/IEC are widely used in the scientific and industrial fields to explore the separation of small and large molecules. Accordingly, more and more new materials, such as Ionic Liquids (ILs), Carbon Dots (CDs), Graphene (GR), Metal Organic Frameworks (MOFs), and covalent bond organic frameworks (COFs), have been developed and used as stationary phases due to their excellent characteristics. Nevertheless, in developing mixed mode stationary phases integrated with new materials, there are some inevitable problems including complicated experimental procedures, stringent synthesis conditions, time consuming cycles, non-uniform morphology and broad particle size distribution. These undesirable defects present inconveniences and obstacles to their further use. Therefore, the method is simple and convenient to prepare the novel mixed mode stationary phase which has the advantages of uniform appearance, high specific surface area, narrow pore size distribution, good thermal stability, good dispersibility and the like, is combined with a novel material, and has important significance for promoting the wide application of the novel mixed mode stationary phase.
The quality of the stationary phase depends on the microsphere material and the functional groups bonded on the surface of the microsphere material to a great extent, and the silica gel stationary phase becomes an ideal separation material for efficiently separating various target analytes due to the capability of bonding various functional groups, providing various interactions and maintaining good stability. At present, various silica gel chromatography packing materials have been reported and widely used, since the selectivity and separation performance of the silica gel stationary phase can be adjusted by surface modification of specific functional groups, thereby achieving a desired separation effect.
Gels generally exhibit semi-solid materials and in some respects exhibit certain advantages over liquids and solids. Gels based on low molecular weight organic gelators (LMOG) are generally considered supramolecular or molecular gels in which organic molecules (typically having a molecular weight of less than 3000) self-assemble into three-dimensional (3D) networks through non-covalent interactions such as hydrogen bonding, pi-pi stacking, electrostatic interactions, van der waals forces, and hydrophobic interactions. Due to the soft colloidal material consisting of the self-assembled fiber network of the molecular gel, the molecular gel attracts wide attention in various potential applications in various fields. However, when the pure dendritic organic small molecule gel is used as a stationary phase, the shape is not uniform, the particle size distribution is wide, the selectivity is poor, the column efficiency is low, the back pressure is high, and the wide application of the pure dendritic organic small molecule gel is seriously hindered.
The invention content is as follows:
in order to solve the problems, the invention designs a preparation method of a dendritic organic small molecular gel silicon-based stationary phase material based on benzyl ether, spherical silicon dioxide is used as a matrix, dendritic organic small molecular gel is used as a modified material, a stationary phase composite material is reasonably designed and conveniently prepared, the advantages of silicon dioxide microspheres and dendritic organic small molecular gel are integrated, the limitation of pure dendritic organic small molecular gel is overcome, the preparation process is simple, and the application prospect is wide.
Dendritic organic small molecular gel silicon-based stationary phase material based on benzyl ether and SiO 2 Taking the amino silica gel as a carrier, carrying out amination reaction on the amino silica gel and cyanuric chloride, and then carrying out continuous alkylation reaction on the amino silica gel and third generation dendritic organogel molecules G3 based on 5-benzyl ether dimethyl isophthalate to graft G3 on the surface of silicon dioxide to form a light yellow powdery dendritic organic micromolecular gel silicon-based fixed phase material SiO based on benzyl ether 2 -G3; wherein G3 is a large monodisperse surrounded by isophthalic acid bisMethyl ester functionalized dendritic organogels, said gels being free of amide or long alkyl chains.
The invention designs a preparation method of a dendritic organic small molecule gel silicon-based stationary phase material based on benzyl ether, which comprises the following steps:
(1) preparation of dimethyl 5-benzyl ether isophthalate G1: dissolving 0.5-1.5 mL of benzyl alcohol, 1-2 g of 5-hydroxyisophthalic acid dimethyl ester and 2-3 g of triphenylphosphine in 10-40 mL of tetrahydrofuran to obtain a first mixed solution; dropwise adding 1-3 mL of diisopropyl azodicarboxylate into the first mixed solution to obtain a second mixed solution, stirring the second mixed solution for 12-32 hours at 25-50 ℃ in a nitrogen atmosphere, purifying by column chromatography after the reaction is finished, spin-drying, and drying at room temperature to obtain needle-like white 5-benzyl ether dimethyl isophthalate G1;
(2) preparation of 5-benzyl ether m-benzenedimethanol G1-CH 2 OH: mixing 1.5-1.9 g of lithium aluminum hydride and 10-50 mL of tetrahydrofuran to obtain a suspension, mixing 0.4-0.6 g G1 obtained in the step (1) with 10-50 mL of tetrahydrofuran to obtain a third mixed solution, dropwise adding the third mixed solution into the suspension at 0 ℃ to obtain a fourth mixed solution, stirring and refluxing the fourth mixed solution at 70-90 ℃ for 1-3 h under a nitrogen atmosphere, and dropwise adding 0.5-2 mLH 2 Stopping the reaction by using O and 0.5-2 mL of 15% NaOH solution, filtering, concentrating the filtrate under reduced pressure, and drying to obtain an off-white solid G1-CH 2 OH; washing the precipitate with tetrahydrofuran to obtain a solid product, and adding 100mLH to the solid product 2 Dissolving O to obtain a fifth mixed solution, adding ethyl acetate dropwise into the fifth mixed solution for extraction, combining organic layers after extraction is finished, drying, spinning, and standing to obtain an off-white solid G1-CH remained in a solid product obtained by precipitation 2 OH; the two fractions obtained were combined to give G1-CH as an off-white solid 2 OH merging;
(3) preparation of a second generation dendritic organogel molecule based on dimethyl 5-benzyl ether isophthalate G2: 2 to 4g of 5-hydroxy isophthalic acid dimethyl ester, 3.5 to 4.5g of triphenylphosphine and 0.5 to 1.5g of G1-CH prepared in the step (2) 2 OH is dissolved in 10-40 mL tetrahydrofuran to obtain a sixth mixture, and 2 to E is added dropwise to the sixth mixture4.5mL of diisopropyl azodicarboxylate to obtain a seventh mixed solution, stirring the seventh mixed solution for 12-32 h at 25-50 ℃ in a nitrogen atmosphere, purifying by using a column chromatography after the reaction is finished, spin-drying, and drying at room temperature to obtain a needle-like white second-generation dendritic organogel molecule G2 based on 5-benzyl ether dimethyl isophthalate;
(4) preparation of hydroxylated G2 organogel molecule G2-CH 2 OH: mixing 0.5-1.5 g of lithium aluminum hydride and 20-50 mL of tetrahydrofuran to obtain a suspension, mixing 3.24-3.72 g G2 obtained in the step (3) with 20-50 mL of tetrahydrofuran to obtain an eighth mixed solution, dropwise adding the eighth mixed solution into the suspension at 0 ℃ to obtain a ninth mixed solution, stirring and refluxing the ninth mixed solution at 70-90 ℃ for 1-3 h under a nitrogen atmosphere, and dropwise adding 0.5-2 mLH 2 Stopping the reaction by using O and 0.5-2 mL of 15% NaOH solution, filtering, concentrating the filtrate under reduced pressure, and drying to obtain an off-white solid G2-CH 2 OH; washing the precipitate with tetrahydrofuran to obtain a solid product, and adding 100mLH to the solid product 2 Dissolving O to obtain a tenth mixed solution, adding ethyl acetate dropwise into the tenth mixed solution for extraction, combining organic layers after extraction is finished, drying, spinning, standing to obtain off-white solid G2-CH remained in the solid product obtained by precipitation 2 OH; the two fractions obtained were combined to give G2-CH as an off-white solid 2 OH merging;
(5) preparation of third generation dendritic organogel molecule based on dimethyl 5-benzyl ether isophthalate G3: 1.4 to 1.9g of 5-hydroxyisophthalic acid dimethyl ester, 2.2 to 2.34g of triphenylphosphine and 0.5 to 1.5g G2-CH prepared in the step (4) 2 Dissolving OH into 30-60 mL of tetrahydrofuran to obtain an eleventh mixed solution, dropwise adding 1.4-1.9 mL of diisopropyl azodicarboxylate into the eleventh mixed solution to obtain a twelfth mixed solution, stirring the twelfth mixed solution for 12-32 hours at 25-50 ℃ in a nitrogen atmosphere, adding tert-butyl methyl ether into the twelfth mixed solution under vigorous stirring after the reaction is finished, and filtering, separating and precipitating; redissolving the precipitate in tetrahydrofuran, precipitating with methanol, and filtering to obtain white third generation dendritic organogel molecule G3 based on dimethyl 5-benzyl ether isophthalate;
(6) preparation of silicon dioxide-dendritic organic micromolecular gel composite material SiO 2 -G3: mixing 0.5-1.5 g of amino silica gel dispersed in 10-40 mL of anhydrous dichloromethane and 0.2-0.6 g of cyanuric chloride to obtain a thirteenth mixed solution, stirring and heating at 20-50 ℃ for 10-40 min, and then adding 0.3-0.8 g G3 and 0.4-0.8 g of AlCl prepared in the step (5) 3 Stirring the fourteenth mixed solution at 40-60 ℃ for 8-24 h to obtain a fourteenth mixed solution, cooling to room temperature after the reaction is finished, washing with dichloromethane, methanol and water respectively, centrifuging for 3min, and vacuum-drying at 110-160 ℃ for 6-24 h to obtain a light yellow powdery silicon dioxide-dendritic organic small molecular gel composite material SiO 2 -G3。
Preferably, in the step (1): 1mL of benzyl alcohol, 1.5g of dimethyl 5-hydroxyisophthalate, 2.5g of triphenylphosphine, 30mL of tetrahydrofuran, and 2mL of diisopropyl azodicarboxylate, and the second mixture was stirred at 40 ℃ under a nitrogen atmosphere for 24 hours.
Preferably, in the step (2): 1.7g of lithium aluminum hydride and 40mL of tetrahydrofuran are used for preparing the suspension; preparing a third mixture solution containing 0.5G of G1 and 40mL of tetrahydrofuran, stirring and refluxing the fourth mixture solution at 0 deg.C and 80 deg.C under nitrogen atmosphere for 2h, and adding dropwise 1mLH 2 The reaction was stopped with O and 1mL of 15% NaOH solution.
Preferably, in the step (3): 1.5G of dimethyl 5-hydroxyisophthalate, 3.2G of triphenylphosphine, and G1-CH 2 1g of OH, 20mL of tetrahydrofuran and 2.5mL of diisopropyl azodicarboxylate, and the seventh mixed solution was stirred at 40 ℃ for 24 hours under a nitrogen atmosphere.
Preferably, in the step (4): 1g of lithium aluminum hydride and 40mL of tetrahydrofuran are used for preparing the suspension; preparing third mixture with G1 of 3.62G and tetrahydrofuran of 40mL, stirring and refluxing the fourth mixture at 0 deg.C under nitrogen atmosphere at 80 deg.C for 2h, and adding dropwise 1mLH 2 The reaction was stopped with O and 1mL of 15% NaOH solution.
Preferably, in the step (5): 1.8G of dimethyl 5-hydroxyisophthalate, 2.24G of triphenylphosphine, and G1-CH 2 OH 1.0g, tetrahydrofuran 50mL, diisopropyl azodicarboxylate 1.8mL, the seventh mixture was stirred at 40 ℃ for 24h under a nitrogen atmosphere.
Preferably, in the step (6): stirring and heating the thirteenth mixed solution for 30min at the temperature of 30 ℃ with 30mL of anhydrous dichloromethane, 1g of amino silica gel and 0.5g of cyanuric chloride; G3G in the preparation of the fourteenth mixed solution, AlCl 3 0.4-0.8 g, stirring the fourteenth mixed solution at 50 ℃ for 16h, and vacuum drying at 140 ℃ for 12 h.
Preferably, the tetrahydrofuran used in steps (1) to (5) is anhydrous tetrahydrofuran.
Preferably, in the step (2) and the step (4), the organic layer is dried using sodium sulfate or anhydrous magnesium sulfate; the step (2) further comprises dropwise adding 0.5-2 mLH 2 O and 0.5-2 mL of 15% NaOH solution are added dropwise to stop the reaction, and 2mLH is added dropwise 2 The O reacts completely with the remaining lithium aluminum hydride.
The invention has the following beneficial effects: the dendritic organic small molecule gel G3 is a promising three-dimensional network compound, G3 is a large monodisperse poly (benzyl ether) dendritic organic gel with the periphery functionalized by dimethyl isophthalate (DMIP) and no amide or long alkyl chain, the gelation characteristics of the gel are highly dependent on the nature of peripheral groups and a dendritic structure, and the high order and unique spatial structure of the gel shows huge potential and advantages in the field of adsorption and separation because the multiple strong pi-pi stacking interaction of peripheral DMIP motifs is a key factor for forming self-assembly gel. In the invention, benzyl alcohol and 5-hydroxy-m-xylylene are used as starting materials to prepare dendritic third-generation organic small molecular gel G3, and G3 is grafted on the surface of silicon dioxide to prepare SiO through continuous Friedel-Craft reaction between Cyanuric Chloride (CC) and G3 2 -G3. Synthesizing a novel dendritic organic micromolecular gel stationary phase, silicon dioxide-dendritic organic micromolecular gel composite material (SiO) 2 -G3) can be used as a novel mixed mode packing and solid phase extraction packing for HPLC. Since a large number of benzene rings, ether groups, methyl groups, lipid groups and carbonyl groups coexist in G3, and hydrophilic triazine moieties are introduced during the grafting process, the developed chromatographic column shows flexible selectivity, enhanced separation performance and flexible application, and can pass throughDifferent flow phase ratios were adjusted for separation of different polar compounds in three chromatographic modes of hydrophilic interaction liquid chromatography (HILIC)/Reverse Phase Liquid Chromatography (RPLC))/ion exchange chromatography (IEX).
The invention also provides an application of the dendritic organic small molecule gel silicon-based stationary phase material based on benzyl ether, which comprises the following steps: on one hand, the silica gel stationary phase material prepared by the method is filled in a stainless steel column with the length of 150mm and the inner diameter of 4.6mm, and the obtained chromatographic column is used for analyzing and separating samples; on the other hand, it is packed in a solid phase extraction cartridge for enrichment of the sample.
Description of the drawings:
FIG. 1 is a structural diagram of a silica-dendritic organic small molecule gel composite material.
FIG. 2 is a NMR H spectrum of G1.
FIG. 3 is G1-CH 2 NMR H spectrum of OH.
FIG. 4 is a NMR H spectrum of G2.
FIG. 5 is a NMR H spectrum of G3.
FIG. 6 is a diagram of the chromatographic separation of several nucleoside and nucleobase mixtures on a column in HILIC mode.
FIG. 7 is a graph of the chromatographic separation of several mixtures of mono-substituted benzenes in the column in RPLC mode.
FIG. 8 is a diagram of the chromatographic separation of several benzoic acid mixtures on a chromatographic column in IEC mode.
FIG. 9 is a chromatogram of the eluate of biphenyl in lake water samples.
The specific implementation mode is as follows:
in order to make the technical scheme of the invention easier to understand, the preparation method and the application of the silica-dendritic organic small molecule gel composite material designed by the invention are clearly and completely described by using a specific embodiment mode.
A preparation method of a dendritic organic small molecule gel silicon-based stationary phase material based on benzyl ether comprises the following steps:
example 1:
the preparation method of the dendritic organic small molecule gel silicon-based stationary phase material based on benzyl ether in the embodiment comprises the following steps:
(1) preparation of dimethyl 5-benzyl ether isophthalate G1: dissolving 0.5mL of benzyl alcohol, 1g of 5-hydroxyisophthalic acid dimethyl ester and 2g of triphenylphosphine in 10mL of anhydrous tetrahydrofuran to obtain a first mixed solution; dropwise adding 1mL of diisopropyl azodicarboxylate into the first mixed solution to obtain a second mixed solution, stirring the second mixed solution at 0 ℃ for 5min, then stirring the second mixed solution at 25 ℃ for 1h in a nitrogen atmosphere, purifying the second mixed solution by column chromatography after the reaction is finished, spin-drying the second mixed solution, and drying the second mixed solution at room temperature to obtain an acicular white solid G1;
(2) preparation of 5-benzyl ether m-benzenedimethanol G1-CH 2 OH: mixing 1.5g of lithium aluminum hydride and 10mL of anhydrous tetrahydrofuran to obtain a suspension, mixing 0.4g G1 obtained in step (1) with 10mL of anhydrous tetrahydrofuran to obtain a third mixed solution, dropwise adding the third mixed solution into the suspension at 0 ℃ to obtain a fourth mixed solution, stirring and refluxing the fourth mixed solution at 70 ℃ for 1h under a nitrogen atmosphere, and dropwise adding 0.5mLH 2 O and 0.5mL of 15% NaOH solution are added dropwise to terminate the reaction, and 2mLH is added dropwise 2 Completely reacting O with the rest lithium aluminum hydride, filtering, concentrating the filtrate under reduced pressure and drying to obtain off-white solid G1-CH 2 OH; washing the precipitate with tetrahydrofuran to obtain solid product; washing the precipitate with anhydrous tetrahydrofuran to obtain a solid product, and adding 100mLH to the solid product 2 Dissolving O to obtain a fifth mixed solution, adding ethyl acetate dropwise into the fifth mixed solution for extraction, combining organic layers after extraction is finished, drying, spinning, standing to obtain off-white solid G1-CH remained in the solid product obtained by precipitation 2 OH; the two fractions obtained were combined to give G1-CH as an off-white solid 2 OH merging;
(3) preparation of a second generation dendritic organogel molecule based on dimethyl 5-benzyl ether isophthalate G2: 2g of dimethyl 5-hydroxyisophthalate, 3.5g of triphenylphosphine and 0.5g G1-CH prepared in step (2) 2 Dissolving OH into 10mL of anhydrous tetrahydrofuran to obtain a sixth mixed solution, dropwise adding 2mL of diisopropyl azodicarboxylate into the sixth mixed solution to obtain a seventh mixed solution, stirring the seventh mixed solution at 0 ℃ for 5min, and then stirring in a nitrogen atmosphereStirring for 12h at the temperature of 25 ℃, purifying by using a column chromatography after the reaction is finished, spin-drying, and drying at room temperature to obtain a needle-like white second-generation dendritic organogel molecule G2 based on 5-benzyl ether dimethyl isophthalate;
(4) preparation of hydroxylated G2 organogel molecule G2-CH 2 OH: mixing 0.5g lithium aluminum hydride and 20mL tetrahydrofuran to obtain suspension, mixing 3.24g G2 obtained in step (3) with 20mL tetrahydrofuran to obtain eighth mixed solution, adding dropwise the eighth mixed solution into the suspension at 0 deg.C to obtain ninth mixed solution, stirring and refluxing the ninth mixed solution at 70 deg.C under nitrogen atmosphere for 1h, and adding dropwise 0.5mLH 2 Stopping the reaction by using O and 0.5mL of 15% NaOH solution, filtering, concentrating the filtrate under reduced pressure and drying to obtain off-white solid G2-CH 2 OH; washing the precipitate with tetrahydrofuran to obtain a solid product, and adding 100mLH to the solid product 2 Dissolving O to obtain a tenth mixed solution, adding ethyl acetate dropwise into the tenth mixed solution for extraction, combining organic layers after extraction is finished, drying, spinning, standing to obtain off-white solid G2-CH remained in the solid product obtained by precipitation 2 OH; the two fractions obtained were combined to give G2-CH as an off-white solid 2 OH merging;
(5) preparation of third generation dendritic organogel molecule based on dimethyl 5-benzyl ether isophthalate G3: 1.4g of dimethyl 5-hydroxyisophthalate, 2.2g of triphenylphosphine and 0.5g G2-CH prepared in step (4) 2 Dissolving OH into 30mL of tetrahydrofuran to obtain an eleventh mixed solution, dropwise adding 1.4mL of diisopropyl azodicarboxylate into the eleventh mixed solution to obtain a twelfth mixed solution, stirring the twelfth mixed solution at 0 ℃ for 5min, then stirring the mixture at 25 ℃ for 12h under a nitrogen atmosphere, after the reaction is finished, adding tert-butyl methyl ether into the twelfth mixed solution under vigorous stirring, and filtering and separating precipitates; redissolving the precipitate in tetrahydrofuran, precipitating with methanol, and filtering to obtain white third generation dendritic organogel molecule G3 based on dimethyl 5-benzyl ether isophthalate;
(6) preparation of silica-dendritic organic micromolecular gel composite material SiO 2 -G3: 0.5g of aminosilicone dispersed in 10mL of anhydrous dichloromethane was reacted with trichloromethaneMixing cyanogen 0.2g to obtain a thirteenth mixture, heating at 20 deg.C under stirring for 10min, and adding the mixture of 0.3g G3 and 0.4g AlCl prepared in step (5) 3 Stirring the fourteenth mixed solution at 40 ℃ for 8h to obtain a fourteenth mixed solution, cooling to room temperature after the reaction is finished, washing with dichloromethane, methanol and water for 3 times respectively, centrifuging at 8000-10000 rpm for 3min, and vacuum drying at 110 ℃ for 6h to obtain light yellow powdery SiO 2 G3 stationary phase material.
Example 2:
the preparation method of the dendritic organic small molecule gel silicon-based stationary phase material based on benzyl ether in the embodiment comprises the following steps:
(1) preparation of dimethyl 5-benzyl ether isophthalate G1: dissolving 1.5mL of benzyl alcohol, 2g of 5-hydroxyisophthalic acid dimethyl ester and 3g of triphenylphosphine in 40mL of anhydrous tetrahydrofuran to obtain a first mixed solution; dropwise adding 3mL of diisopropyl azodicarboxylate into the first mixed solution to obtain a second mixed solution, stirring the second mixed solution at 0 ℃ for 15min, then stirring the second mixed solution at 50 ℃ for 32h in a nitrogen atmosphere, purifying the second mixed solution by column chromatography after the reaction is finished, and drying the second mixed solution to obtain needle-like white 5-benzyl ether dimethyl isophthalate G1;
(2) preparation of 5-benzyl ether m-benzenedimethanol G1-CH 2 OH: mixing 1.9g of lithium aluminum hydride and 50mL of anhydrous tetrahydrofuran to obtain a suspension, mixing 0.6g G1 obtained in the step (1) and 50mL of anhydrous tetrahydrofuran to obtain a third mixed solution, dropwise adding the third mixed solution into the suspension at 0 ℃ to obtain a fourth mixed solution, stirring and refluxing the fourth mixed solution at 90 ℃ for 3 hours under a nitrogen atmosphere, and dropwise adding 2mLH 2 O and 2mL of 15% NaOH solution are added dropwise to terminate the reaction, and 2mLH is added dropwise 2 Completely reacting O with the rest lithium aluminum hydride, filtering, concentrating the filtrate under reduced pressure, and drying to obtain off-white solid G1-CH 2 OH; washing the precipitate with tetrahydrofuran to obtain solid product; washing the precipitate with anhydrous tetrahydrofuran to obtain a solid product, and adding 100mLH to the solid product 2 Dissolving O to obtain a fifth mixed solution, adding ethyl acetate dropwise into the fifth mixed solution for extraction, combining organic layers after extraction is finished, drying, and standing to obtain off-white residue in the solid product obtained by precipitationColored solid G1-CH 2 OH; the two fractions obtained were combined to give G1-CH as an off-white solid 2 OH merging;
(3) preparation of a second generation dendritic organogel molecule based on dimethyl 5-benzyl ether isophthalate G2: 4g of dimethyl 5-hydroxyisophthalate, 4.5g of triphenylphosphine and 1.5g G1-CH prepared in step (2) 2 Dissolving OH into 40mL of anhydrous tetrahydrofuran to obtain a sixth mixed solution, dropwise adding 4.5mL of diisopropyl azodicarboxylate into the sixth mixed solution to obtain a seventh mixed solution, stirring the seventh mixed solution at 0 ℃ for 15min, then stirring the seventh mixed solution at 50 ℃ for 32h in a nitrogen atmosphere, purifying the mixture by using a column chromatography after the reaction is finished, spin-drying the mixture, and drying the mixture at room temperature to obtain needle-like white second-generation dendritic organogel molecules G2 based on 5-benzyl ether dimethyl isophthalate;
(4) preparation of hydroxylated G2 organogel molecule G2-CH 2 OH: mixing 1.5g of lithium aluminum hydride and 50mL of tetrahydrofuran to obtain a suspension, mixing 3.72g G2 obtained in step (3) with 50mL of tetrahydrofuran to obtain an eighth mixed solution, dropwise adding the eighth mixed solution into the suspension at 0 ℃ to obtain a ninth mixed solution, stirring and refluxing the ninth mixed solution at 90 ℃ for 3h under nitrogen atmosphere, and dropwise adding 2mLH 2 Stopping the reaction by using O and 2mL of 15% NaOH solution, filtering, concentrating the filtrate under reduced pressure and drying to obtain off-white solid G2-CH 2 OH; washing the precipitate with tetrahydrofuran to obtain a solid product, and adding 100mLH to the solid product 2 Dissolving O to obtain a tenth mixed solution, adding ethyl acetate dropwise into the tenth mixed solution for extraction, combining organic layers after extraction is finished, drying, spinning, standing to obtain off-white solid G2-CH remained in the solid product obtained by precipitation 2 OH; the two fractions obtained were combined to give G2-CH as an off-white solid 2 OH merging;
(5) preparation of third generation dendritic organogel molecule based on dimethyl 5-benzyl ether isophthalate G3: 1.9g of dimethyl 5-hydroxyisophthalate, 2.34g of triphenylphosphine and 1.5g G2-CH prepared in step (4) 2 Dissolving OH in 60mL tetrahydrofuran to obtain an eleventh mixed solution, adding 1.9mL diisopropyl azodicarboxylate dropwise to the eleventh mixed solution to obtain a twelfth mixed solution, and mixing the twelfth mixed solutionStirring at 0 ℃ for 15min, then stirring at 50 ℃ for 32h under the nitrogen atmosphere, after the reaction is finished, adding tert-butyl methyl ether into the twelfth mixed solution under vigorous stirring, and filtering, separating and precipitating; redissolving the precipitate in tetrahydrofuran, precipitating with methanol, and filtering to obtain white third generation dendritic organogel molecule G3 based on dimethyl 5-benzyl ether isophthalate;
(6) preparation of silica-dendritic organic micromolecular gel composite material SiO 2 -G3: mixing 1.5g of amino silica gel dispersed in 10-40 mL of anhydrous dichloromethane with 0.6g of cyanuric chloride to obtain a thirteenth mixed solution, stirring and heating at 50 ℃ for 40min, and then adding 0.8g G3 and 0.8g of AlCl prepared in the step (5) 3 Stirring the fourteenth mixed solution at 60 ℃ for 24h to obtain a fourteenth mixed solution, cooling to room temperature after the reaction is finished, washing with dichloromethane, methanol and water for 3 times, centrifuging at 8000-10000 rpm for 3min, and vacuum drying at 160 ℃ for 24h to obtain the faint yellow powdered silicon dioxide-dendritic organic small molecular gel composite material SiO 2 -G3。
Example 3:
the preparation method of the dendritic organic small molecule gel silicon-based stationary phase material based on benzyl ether in the embodiment comprises the following steps:
(1) preparation of dimethyl 5-benzyl ether isophthalate G1: dissolving 1mL of benzyl alcohol, 1.5g of dimethyl 5-hydroxyisophthalate and 2.5g of triphenylphosphine in 30mL of tetrahydrofuran to obtain a first mixed solution; dropwise adding 2mL of diisopropyl azodicarboxylate into the first mixed solution to obtain a second mixed solution, stirring the second mixed solution at 0 ℃ for 10min, then stirring the second mixed solution at 40 ℃ for 24h in a nitrogen atmosphere, purifying the second mixed solution by column chromatography after the reaction is finished, spin-drying the second mixed solution, and drying the second mixed solution at room temperature to obtain needle-like white solid dimethyl 5-benzyl ether isophthalate G1;
(2) preparation of 5-benzyl ether m-benzenedimethanol G1-CH 2 OH: mixing 1.7g of lithium aluminum hydride and 40mL of tetrahydrofuran to obtain a suspension, mixing 0.5g G1 obtained in the step (1) with 40mL of tetrahydrofuran to obtain a third mixed solution, dropwise adding the third mixed solution into the suspension at 0 ℃ to obtain a fourth mixed solution, and adding the fourth mixed solution into the suspensionStirring and refluxing for 2h at 80 ℃ under nitrogen atmosphere, and dropwise adding 1mLH 2 O and 1mL of 15% NaOH solution are added dropwise to terminate the reaction, and 2mLH is added dropwise 2 Completely reacting O with the rest lithium aluminum hydride, filtering, concentrating the filtrate under reduced pressure, and drying to obtain off-white solid G1-CH 2 OH; washing the precipitate with tetrahydrofuran to obtain solid product; washing the precipitate with anhydrous tetrahydrofuran to obtain a solid product, and adding 100mLH to the solid product 2 Dissolving O to obtain a fifth mixed solution, adding ethyl acetate dropwise into the fifth mixed solution for extraction, combining organic layers after extraction is finished, drying, spinning, standing to obtain off-white solid G1-CH remained in the solid product obtained by precipitation 2 OH; the two fractions obtained were combined to give G1-CH as an off-white solid 2 OH merging;
(3) preparation of a second generation dendritic organogel molecule based on dimethyl 5-benzyl ether isophthalate G2: dissolving 1.5G of 5-hydroxy dimethyl isophthalate, 3.2G of triphenylphosphine and 1G G1-CH2OH prepared in the step (2) into 20mL of tetrahydrofuran to obtain a sixth mixed solution, dropwise adding 2.5mL of diisopropyl azodicarboxylate into the sixth mixed solution to obtain a seventh mixed solution, stirring the seventh mixed solution at 0 ℃ for 10min, then stirring at 40 ℃ for 24h under a nitrogen atmosphere, purifying by using a column chromatography after the reaction is finished, spin-drying, and drying at room temperature to obtain a white needle-shaped solid, namely a second generation dendritic organogel molecule G2 based on 5-benzyl ether dimethyl isophthalate;
(4) preparation of hydroxylated G2 organogel molecule G2-CH 2 OH: mixing 1.0g of lithium aluminum hydride and 40mL of tetrahydrofuran to obtain a suspension, mixing 3.62g G2 obtained in step (3) with 40mL of tetrahydrofuran to obtain an eighth mixed solution, dropwise adding the eighth mixed solution into the suspension at 0 ℃ to obtain a ninth mixed solution, stirring and refluxing the ninth mixed solution at 80 ℃ for 2h under nitrogen atmosphere, and dropwise adding 1mLH 2 Stopping the reaction by using O and 1mL of 15% NaOH solution, filtering, concentrating the filtrate under reduced pressure and drying to obtain off-white solid G2-CH 2 OH; washing the precipitate with tetrahydrofuran to obtain a solid product, and adding 100mLH to the solid product 2 Dissolving O to obtain a tenth mixed solution, adding ethyl acetate dropwise into the tenth mixed solution for extraction, and combining organic layers after extraction is finishedDrying, spin-drying, and standing to obtain off-white solid G2-CH remaining in the solid product obtained by precipitation 2 OH; the two fractions obtained were combined to give G2-CH as an off-white solid 2 OH merging;
(5) preparation of a third generation dendritic organogel molecule based on dimethyl 5-benzyl ether isophthalate G3: 1.8g of dimethyl 5-hydroxyisophthalate, 2.24g of triphenylphosphine and 1g G2-CH prepared in step (4) 2 Dissolving OH into 50mL of tetrahydrofuran to obtain an eleventh mixed solution, dropwise adding 1.8mL of diisopropyl azodicarboxylate into the eleventh mixed solution to obtain a twelfth mixed solution, stirring the twelfth mixed solution at 0 ℃ for 10min, then stirring the twelfth mixed solution at 40 ℃ for 24h under a nitrogen atmosphere, after the reaction is finished, adding tert-butyl methyl ether into the twelfth mixed solution under vigorous stirring, and filtering and separating precipitates; redissolving the precipitate in tetrahydrofuran, precipitating with methanol, and filtering to obtain a white solid third generation dendritic organogel molecule G3 based on dimethyl 5-benzyl ether isophthalate;
(6) preparation of silicon dioxide-dendritic organic micromolecular gel composite material SiO 2 -G3: mixing 1g of amino silica gel dispersed in 30mL of anhydrous dichloromethane with 0.5g of cyanuric chloride to obtain a thirteenth mixture, heating while stirring at 30 deg.C for 30min, and adding 0.4g G3 prepared in step (5) and 0.5g of AlCl 3 Stirring the fourteenth mixed solution at 50 ℃ for 16h, cooling to room temperature after the reaction is finished, washing with dichloromethane, methanol and water for 3 times respectively, centrifuging at 8000-10000 rpm for 3min, and vacuum drying at 140 ℃ for 12h to obtain the light yellow powdery silicon dioxide-dendritic organic small molecular gel composite material SiO 2 -G3。
SiO modified by novel dendritic organic gel G3 by adopting element analysis 2 The stationary phase was characterized. Dendritic organic gel G3 modified SiO 2 Stationary phase, dendritic organic molecule gel G3 and SiO 2 -NH 2 The elemental analysis of (2) is shown in Table 1. With SiO 2 -NH 2 Compared with the SiO modified by the dendritic organic gel G3 2 C, N and H content were significantly increased by 29.35%, 3.05% and 2.57%, respectively. This is achieved bySuccessful immobilization of the dendrimer gelator on silica was confirmed.
Table 1: g3, SiO 2 -NH 2 And SiO 2 Elemental analysis data of G3
| Sample (I) | C％ | N％ | H％ |
| G3 | 63.44 | 0 | 4.23 |
| SiO 2 -NH 2 | 8.27 | 1.53 | 1.78 |
| SiO 2 -G3 | 29.35 | 3.05 | 2.57 |
The invention discloses an application of a silicon-based stationary phase material of a dendritic organic small molecular gel based on benzyl ether, which comprises the following specific embodiments:
application example 1:
(1) the dendritic organic small molecule gel silicon-based stationary phase prepared in example 3 was filled in a stainless steel column 150mm in length and 4.6mm in inner diameter by a homogenization method, and the obtained chromatographic column was used for analyzing and separating samples.
(2) The dendritic organic small molecular gel silicon-based stationary phase prepared in the example 3 is filled in a solid phase extraction column, and the obtained solid phase extraction column is used for enriching samples.
Using the column prepared in this application example, several nucleoside and nucleobase mixtures were separated in HILIC mode. The chromatographic separation results are shown in figure 2: 1 is thiourea, 2 is thymine, 3 is adenine, 4 is inosine, 5 is cytosine, and 6 is guanosine. The chromatographic conditions are as follows: acetonitrile/water (80/20, v/v); the flow rate is 1 mL/min; the detection wavelength is 260 nm. As can be seen from FIG. 2, the stationary phase prepared by the present invention has a good separation effect on the mixture of nucleoside and nucleobase in HILIC mode.
Application example 2:
(1) the dendritic organic small molecule gel silicon-based stationary phase prepared in example 3 was filled in a stainless steel column having a length of 150mm and an inner diameter of 4.6mm by a homogenization method, and the obtained chromatographic column was used for analyzing and separating a sample.
(2) The dendritic organic small molecule gel silicon-based stationary phase prepared in the example 3 is filled in a solid phase extraction small column, and the obtained solid phase extraction small column is used for enriching samples.
Several monosubstituted benzene mixtures were separated in RPLC mode using the column prepared in this application example. The chromatographic separation results are shown in fig. 3: 1 is phenol, 2 is toluene, 3 is chlorobenzene, 4 is benzaldehyde, 5 is acetophenone and 6 is nitrobenzene. The chromatographic conditions are acetonitrile/water (80/20, v/v); the flow rate is 1 mL/min; the detection wavelength is 254 nm. From FIG. 3, it can be seen that the stationary phase prepared by the present invention has a good separation effect on the mono-substituted benzene mixture in the RPLC mode.
Application example 3:
(1) the dendritic organic small molecule gel silicon-based stationary phase prepared in example 3 was filled in a stainless steel column having a length of 150mm and an inner diameter of 4.6mm by a homogenization method, and the obtained chromatographic column was used for analyzing and separating a sample.
(2) The dendritic organic small molecule gel silicon-based stationary phase prepared in the example 3 is filled in a solid phase extraction small column, and the obtained solid phase extraction small column is used for enriching samples.
Several benzoic acid mixtures were separated in IEC mode using the column prepared in this application example. The chromatographic separation results are shown in figure 4: 1 is benzoic acid, 2 is 2, 5-dihydroxy terephthalic acid, and 3 is 1,3, 5-benzene tricarboxylic acid. Acetonitrile/water (80/20, v/v); the flow rate is 1 mL/min; the detection wavelength was 240 nm. It can be seen from fig. 4 that the stationary phase prepared by the present invention has a good separation effect on the benzoic acid mixture in IEC mode.
Application example 4:
the solid phase extraction cartridge prepared in example 3 was used, the flow rate was controlled and the cartridge was activated with 3mL of acetonitrile; then, 5mL of a 30 mu g/mL biphenyl lake water standard sample flows through the solid phase extraction column by controlling the flow rate; finally, elution was with 3mL acetonitrile. The eluate was filtered through a 0.22 μm filter and subjected to HPLC detection. The chromatographic conditions are acetonitrile/water (80/20, v/v); the flow rate is 1 mL/min; the detection wavelength is 254 nm. The results of the measurements were substantially consistent with the actual concentration of biphenyl in the lake water samples, and the results are shown in fig. 5 and table 1.
Table 2: results of measurement and analysis of Biphenyl in lake Water samples
It should be noted that the embodiments described herein are only some embodiments of the present invention, and not all implementations of the present invention, and the embodiments are only examples, which are only used to provide a more intuitive and clear understanding of the present invention, and are not intended to limit the technical solutions of the present invention. All other embodiments, as well as other simple substitutions and various changes to the technical solutions of the present invention, which can be made by those skilled in the art without inventive work, are within the scope of the present invention without departing from the spirit of the present invention.
Claims (10)
1. The benzyl ether-based dendritic organic small molecule gel silicon-based stationary phase material is characterized in that SiO is used as the benzyl ether-based dendritic organic small molecule gel silicon-based stationary phase material 2 Taking the amino silica gel as a carrier, carrying out amination reaction on the amino silica gel and cyanuric chloride, and then carrying out continuous alkylation reaction on the amino silica gel and third generation dendritic organogel molecules G3 based on 5-benzyl ether dimethyl isophthalate to graft G3 on the surface of silicon dioxide to form a light yellow powdery dendritic organic micromolecular gel silicon-based fixed phase material SiO based on benzyl ether 2 -G3; wherein G3 is a large monodisperse, dimethyl isophthalate functionalized arborescent organogel peripherally, said gel being free of amide or long alkyl chains.
2. A preparation method of a dendritic organic small molecule gel silicon-based stationary phase material based on benzyl ether is characterized by comprising the following steps:
(1) preparation of dimethyl 5-benzyl ether isophthalate G1: dissolving 0.5-1.5 mL of benzyl alcohol, 1-2 g of 5-hydroxyisophthalic acid dimethyl ester and 2-3 g of triphenylphosphine in 10-40 mL of tetrahydrofuran to obtain a first mixed solution; dropwise adding 1-3 mL of diisopropyl azodicarboxylate into the first mixed solution to obtain a second mixed solution, stirring the second mixed solution for 12-32 hours at 25-50 ℃ in a nitrogen atmosphere, purifying by column chromatography after the reaction is finished, and drying to obtain needle-like white 5-benzyl ether dimethyl isophthalate G1;
(2) preparation of 5-benzyl ether m-benzenedimethanol G1-CH 2 OH: mixing 1.5-1.9 g of lithium aluminum hydride and 10-50 mL of tetrahydrofuran to obtain a suspension, mixing 0.4-0.6 g G1 obtained in the step (1) with 10-50 mL of tetrahydrofuran to obtain a third mixed solution, dropwise adding the third mixed solution into the suspension at 0 ℃ to obtain a fourth mixed solution, stirring and refluxing the fourth mixed solution at 70-90 ℃ for 1-3 h under a nitrogen atmosphere, and dropwise adding 0.5-2 mLH 2 Stopping the reaction by using O and 0.5-2 mL of 15% NaOH solution, filtering, concentrating the filtrate under reduced pressure, and drying to obtain an off-white solid G1-CH 2 OH; washing the precipitate with tetrahydrofuran to obtain a solid product, and adding 100mLH to the solid product 2 Dissolving O to obtain a fifth mixed solution, adding ethyl acetate dropwise into the fifth mixed solution for extraction, combining organic layers after extraction is finished, drying, and standing to obtain off-white solid G1-CH remained in the solid product obtained by precipitation 2 OH; the two fractions obtained were combined to give G1-CH as an off-white solid 2 OH merging;
(3) preparation of a second generation dendritic organogel molecule based on dimethyl 5-benzyl ether isophthalate G2: 2 to 4g of 5-hydroxy isophthalic acid dimethyl ester, 3.5 to 4.5g of triphenylphosphine and 0.5 to 1.5g G1-CH prepared in the step (2) 2 Dissolving OH into 10-40 mL of tetrahydrofuran to obtain a sixth mixed solution, dropwise adding 2-4.5 mL of diisopropyl azodicarboxylate into the sixth mixed solution to obtain a seventh mixed solution, stirring the seventh mixed solution at 25-50 ℃ for 12-32 h in a nitrogen atmosphere, purifying by using column chromatography after the reaction is finished, and drying to obtain needle-like white second-generation dendritic organogel molecules G2 based on 5-benzyl ether dimethyl isophthalate;
(4) preparation of hydroxylated G2 organogel molecule G2-CH 2 OH: mixing 0.5-1.5 g of lithium aluminum hydride and 20-50 mL of tetrahydrofuran to obtain a suspension, mixing 3.24-3.72 g G2 obtained in the step (3) with 20-50 mL of tetrahydrofuran to obtain an eighth mixed solution, dropwise adding the eighth mixed solution into the suspension at 0 ℃ to obtain a ninth mixed solution, stirring and refluxing the ninth mixed solution at 70-90 ℃ for 1-3 h under a nitrogen atmosphere, and dropwise adding 0.5-2 mLH 2 Stopping the reaction by using O and 0.5-2 mL of 15% NaOH solution, filtering, concentrating the filtrate under reduced pressure, and drying to obtain an off-white solid G2-CH 2 OH; washing the precipitate with tetrahydrofuran to obtain a solid product, and adding 100mLH to the solid product 2 Dissolving O to obtain a tenth mixed solution, adding ethyl acetate dropwise into the tenth mixed solution for extraction, combining organic layers after extraction is finished, drying, and standing to obtain off-white solid G2-CH remained in the solid product obtained by precipitation 2 OH; the two fractions obtained were combined to give G2-CH as an off-white solid 2 OH merging;
(5) preparation of third generation dendritic organogel molecule based on dimethyl 5-benzyl ether isophthalate G3: 1.4 to 1.9g of dimethyl 5-hydroxyisophthalate, 2.2 to 2.34g of triphenylphosphine and0.5-1.5 g G2-CH prepared in step (4) 2 Dissolving OH into 30-60 mL of tetrahydrofuran to obtain an eleventh mixed solution, dropwise adding 1.4-1.9 mL of diisopropyl azodicarboxylate into the eleventh mixed solution to obtain a twelfth mixed solution, stirring the twelfth mixed solution for 12-32 hours at 25-50 ℃ in a nitrogen atmosphere, adding tert-butyl methyl ether into the twelfth mixed solution under vigorous stirring after the reaction is finished, and filtering, separating and precipitating; re-dissolving the obtained precipitate in tetrahydrofuran, precipitating with methanol, and filtering to obtain white third generation dendritic organic gel molecule G3 based on dimethyl 5-benzyl ether isophthalate;
(6) preparation of silica-dendritic organic micromolecular gel composite material SiO 2 -G3: mixing 0.5-1.5 g of amino silica gel dispersed in 10-40 mL of anhydrous dichloromethane and 0.2-0.6 g of cyanuric chloride to obtain a thirteenth mixed solution, stirring and heating at 20-50 ℃ for 10-40 min, and then adding 0.3-0.8 g G3 and 0.4-0.8 g of AlCl prepared in the step (5) 3 Stirring the fourteenth mixed solution at 40-60 ℃ for 8-24 h to obtain a fourteenth mixed solution, cooling to room temperature after the reaction is finished, washing with dichloromethane, methanol and water respectively, centrifuging for 3min, and vacuum-drying at 110-160 ℃ for 6-24 h to obtain the silica-dendritic organic small molecular gel composite material SiO 2 -G3。
3. The method of claim 2, wherein in step (1): 1mL of benzyl alcohol, 1.5g of dimethyl 5-hydroxyisophthalate, 2.5g of triphenylphosphine, 30mL of tetrahydrofuran, and 2mL of diisopropyl azodicarboxylate, and the second mixture was stirred at 40 ℃ under a nitrogen atmosphere for 24 hours.
4. The method of claim 2, wherein in step (2): 1.7g of lithium aluminum hydride and 40mL of tetrahydrofuran are used for preparing the suspension; preparing a third mixture solution containing 0.5G of G1 and 40mL of tetrahydrofuran, stirring and refluxing the fourth mixture solution at 0 deg.C and 80 deg.C under nitrogen atmosphere for 2h, and adding dropwise 1mLH 2 The reaction was stopped with O and 1mL of 15% NaOH solution.
5. The method of claim 2, wherein in step (3): 1.5G of dimethyl 5-hydroxyisophthalate, 3.2G of triphenylphosphine, and G1-CH 2 1g of OH, 20mL of tetrahydrofuran and 2.5mL of diisopropyl azodicarboxylate, and the seventh mixed solution was stirred at 40 ℃ for 24 hours under a nitrogen atmosphere.
6. The method of claim 2, wherein in step (4): 1g of lithium aluminum hydride and 40mL of tetrahydrofuran are used for preparing the suspension; preparing third mixture with G1 of 3.62G and tetrahydrofuran of 40mL, stirring and refluxing the fourth mixture at 0 deg.C under nitrogen atmosphere at 80 deg.C for 2h, and adding dropwise 1mLH 2 The reaction was stopped with O and 1mL of 15% NaOH solution.
7. The method of claim 2, wherein in step (5): 1.8G of dimethyl 5-hydroxyisophthalate, 2.24G of triphenylphosphine, and G1-CH 2 1g of OH, 50mL of tetrahydrofuran and 1.8mL of diisopropyl azodicarboxylate, and the seventh mixed solution was stirred at 40 ℃ for 24 hours under a nitrogen atmosphere.
8. The method of claim 2, wherein in step (6): stirring and heating the thirteenth mixed solution for 30min at the temperature of 30 ℃ with 30mL of anhydrous dichloromethane, 1g of amino silica gel and 0.5g of cyanuric chloride; in the preparation of the fourteenth mixed solution, G3 is 0.4G, AlCl 3 0.5g of the fourteenth mixture was stirred at 50 ℃ for 16h and dried under vacuum at 140 ℃ for 12 h.
9. The process according to claim 2, wherein the tetrahydrofuran used in steps (1) to (5) is anhydrous tetrahydrofuran.
10. The method according to claim 2, wherein in the steps (2) and (4), the organic layer is dried using sodium sulfate or anhydrous magnesium sulfate; the step (2) further comprises dropwise adding 0.5-2 mLH 2 Stopping with 0.5-2 mL of 15% NaOH solutionAfter the reaction, 2mLH was added dropwise 2 The O reacts completely with the remaining lithium aluminum hydride.
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