CN108786764B - Organic-silica gel hybrid thiophilic monolithic material and preparation method and application thereof - Google Patents
Organic-silica gel hybrid thiophilic monolithic material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 72
- 239000000741 silica gel Substances 0.000 title claims abstract description 62
- 229910002027 silica gel Inorganic materials 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 46
- 239000003999 initiator Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 claims abstract description 19
- UFHILTCGAOPTOV-UHFFFAOYSA-N tetrakis(ethenyl)silane Chemical compound C=C[Si](C=C)(C=C)C=C UFHILTCGAOPTOV-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 12
- 239000004088 foaming agent Substances 0.000 claims abstract description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 26
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 16
- 244000028419 Styrax benzoin Species 0.000 claims description 13
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 13
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 13
- 229960002130 benzoin Drugs 0.000 claims description 13
- 235000019382 gum benzoic Nutrition 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 7
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 229940113115 polyethylene glycol 200 Drugs 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 3
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 claims description 2
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 claims description 2
- DZZAHLOABNWIFA-UHFFFAOYSA-N 2-butoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCCCC)C(=O)C1=CC=CC=C1 DZZAHLOABNWIFA-UHFFFAOYSA-N 0.000 claims description 2
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 claims description 2
- 229940068886 polyethylene glycol 300 Drugs 0.000 claims description 2
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 2
- 229940057847 polyethylene glycol 600 Drugs 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 238000000926 separation method Methods 0.000 abstract description 19
- 150000001875 compounds Chemical class 0.000 abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 11
- 229920000620 organic polymer Polymers 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 26
- 239000011148 porous material Substances 0.000 description 21
- 238000001514 detection method Methods 0.000 description 20
- 238000006116 polymerization reaction Methods 0.000 description 19
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000003361 porogen Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 230000035699 permeability Effects 0.000 description 11
- 239000012086 standard solution Substances 0.000 description 11
- 239000003480 eluent Substances 0.000 description 9
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000012488 sample solution Substances 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000004587 chromatography analysis Methods 0.000 description 5
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 description 5
- 235000011152 sodium sulphate Nutrition 0.000 description 5
- XGKGITBBMXTKTE-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)disulfanyl]phenol Chemical compound C1=CC(O)=CC=C1SSC1=CC=C(O)C=C1 XGKGITBBMXTKTE-UHFFFAOYSA-N 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 230000000717 retained effect Effects 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 238000005251 capillar electrophoresis Methods 0.000 description 2
- 238000001962 electrophoresis Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 125000001174 sulfone group Chemical group 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005429 filling process Methods 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001121 post-column derivatisation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
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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
-
- 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
- B01D15/34—Size selective separation, e.g. size exclusion chromatography, gel filtration, permeation
Abstract
The invention discloses an organic-silica gel hybrid thiophilic monolithic material and a preparation method and application thereof, wherein the preparation method comprises the following steps: in the presence of light and an initiator, divinyl sulfone DVS and tetravinyl silane TVS are subjected to copolymerization reaction in a pore-foaming agent to prepare the organic-silica gel hybrid thiophilic monolithic material Poly (DVS-co-TVS). The organic-silica gel hybrid thiophilic monolithic material has an adjustable 3D framework structure and also has excellent mechanical property and stability; the method has the advantages of organic polymer, silica gel and thiophilic material, so that the method can be applied to enrichment and separation of compounds containing disulfide bonds, and the preparation method has the advantages of simple steps, simple equipment and good reproducibility.
Description
Technical Field
The invention relates to a thiophilic material, in particular to an organic-silica gel hybrid thiophilic monolithic material and a preparation method and application thereof.
Background
The preparation of the monolithic column adopts an in-situ polymerization mode, avoids the complicated processes of filling particles and burning a plunger piston and the like of the packed column, and has higher comparison and column capacity than open columns (see Journal of Chromatography A, No. 954, pages 5-32 in 2002), so the monolithic column has remarkable advantages in the field of capillary research and is widely developed.
The monolithic column can be classified into organic polymer monolithic column, silica gel monolithic column and organic-silica gel monolithic column (refer to Electrophoresis 2011, 32, 105-115). The organic polymer monolithic column has the advantages of wide pH application range and simple preparation, but has easy swelling property and poor stability in an organic solvent. Monolithic silica gel columns have good mechanical strength and stability, but the preparation process is relatively complicated (Journal of Chromatography A, 1271, page 115-123 of 2013), and post-column derivatization is often required. The organic-silica gel hybrid monolithic column has the advantages of both organic polymeric monolithic column materials and inorganic monolithic materials. Thus, organo-silica gel monolithic columns have been rapidly developed.
The preparation method of the organic-silica gel hybrid column mainly comprises a sol-gel method, a one-pot method and other polymerization methods. The sol-gel method (Anal. chem 2949-2956 of 2008 80) is the earliest developed preparation method of the organic-silica gel monolithic column, and has the advantages of simple preparation, good universality and the like; however, this method relies on silane reagents with functional groups, and the types of functionalized silane reagents are limited, thus limiting the application of the sol-gel method. Later, post-modification methods were developed to introduce organic functional groups by reacting organic monomers with reactive groups; however, the post-column modification steps are numerous and are not favorable for the reproducibility of the preparation of the hybrid monolithic column.
Disclosure of Invention
The invention aims to provide an organic-silica gel hybrid thiophilic monolithic material and a preparation method and application thereof, and the organic-silica gel hybrid thiophilic monolithic material has an adjustable 3D framework structure and also has excellent mechanical properties and stability; the method has the advantages of organic polymer, silica gel and thiophilic material, so that the method can be applied to enrichment and separation of compounds containing disulfide bonds, and the preparation method has the advantages of simple steps, simple equipment and good reproducibility.
In order to achieve the above object, the present invention provides a method for preparing an organo-silica gel hybrid thiophilic monolithic material, comprising: in the presence of light and an initiator, divinyl sulfone DVS and tetravinyl silane TVS are subjected to copolymerization reaction in a pore-foaming agent to prepare the organic-silica gel hybrid thiophilic monolithic material Poly (DVS-co-TVS).
The invention also provides an organic-silica gel hybrid thiophilic monolithic material, which is characterized in that the organic-silica gel hybrid thiophilic monolithic material is prepared by the preparation method.
The invention further provides application of the organic-silica gel hybrid thiophilic monolithic material in enrichment and separation of specificity of compounds containing disulfide bonds.
In the above technical scheme, as shown in fig. 1, the organic-inorganic hybrid thiophilic monolithic column material Poly (DVS-co-TVS) is prepared by polymerization under the photoinitiation conditions of divinyl sulfone and tetravinyl silane; the preparation process of the material is easier to control, the obtained organic-inorganic hybrid thiophilic monolithic column material Poly (DVS-co-TVS) has a 3D framework structure, and meanwhile, the material has the advantages of strong mechanical property, good stability, larger specific surface area and permeability, organic polymers, silica gel and thiophilic materials, so that the material can be applied to the enrichment and separation of compounds containing disulfide bonds, and meanwhile, the preparation method has the advantages of simple steps, simple equipment and good reproducibility.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic diagram of the preparation principle of the present invention.
FIG. 2 is a scanning electron micrograph of Poly (DVS-co-TVS) organic-inorganic hybrid thiophilic monolithic material in example 1: a is 1300 times of scanning electron microscope images, b is 3500 times of scanning electron microscope images, and c is 6000 times of scanning electron microscope images;
FIG. 3 is a Fourier transform infrared spectrum of the Poly (DVS-co-TVS) organo-silica hybrid thiophilic monolith in example 1;
FIG. 4 is an energy dispersive X-ray spectroscopy plot of the Poly (DVS-co-TVS) organo-silica hybrid thiophilic monolith in example 1;
FIG. 5 is a thermogravimetric analysis of the Poly (DVS-co-TVS) organo-silica hybrid thiophilic monolith in example 1;
FIG. 6 is a chromatogram of specific separation and enrichment of disulfide bond-containing compounds by the organic-inorganic hybrid thiophilic monolithic material Poly (DVS-co-TVS) in example 1.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a preparation method of an organic-silica gel hybrid thiophilic monolithic material, which comprises the following steps: in the presence of light and an initiator, divinyl sulfone DVS and tetravinyl silane TVS are subjected to copolymerization reaction in a pore-foaming agent to prepare the organic-silica gel hybrid thiophilic monolithic material Poly (DVS-co-TVS).
In the present invention, the amount of each raw material may be selected within a wide range, but in order to further improve the specific surface area and permeability of the obtained organo-silica gel hybrid thiophilic monolithic material, thereby improving the enrichment and separation effect of the disulfide bond-containing compound, it is preferable that the weight ratio of TVS, DVS, porogen is 1: 1-3: 2.1-7.4; more preferably, the weight ratio of TVS to initiator is 1: 0.04-0.15.
In the present invention, the specific kind of the porogen may be selected within a wide range, but in order to further improve the specific surface area and permeability of the prepared organo-silica gel hybrid thiophilic monolithic material, thereby improving the enrichment and separation effect of the disulfide bond-containing compound, preferably, the porogen includes a first porogen selected from at least one of n-propanol, isopropanol, and dimethyl sulfoxide and a second porogen selected from at least one of polyethylene glycol 200, polyethylene glycol 300, polyethylene glycol 400, polyethylene glycol 600, and diethylene glycol diethyl ether. Wherein 200, 300, 400 and 600 after polyethylene glycol refer to the average molecular weight of polyethylene glycol.
In the case where the porogen includes a first porogen and a second porogen, in order to further increase the specific surface area and permeability of the prepared organic-silica gel hybrid thiophilic monolithic material, thereby increasing the enrichment and separation effect of the disulfide bond-containing compound, preferably, the weight ratio of the first porogen to the second porogen is 1: 0.6-2.
In the present invention, the specific kind of the initiator may be selected within a wide range, but in order to further improve the specific surface area and permeability of the resulting organo-silica gel hybrid thiophilic monolith, thereby improving the enrichment and separation effect of the disulfide bond-containing compound, it is preferable that the initiator is selected from at least one of benzoin, benzoin dimethyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin butyl ether.
In the invention, the specific charging sequence can be selected in a wide range, but in order to further improve the specific surface area and permeability of the prepared organic-silica gel hybrid thiophilic monolithic material, thereby improving the enrichment and separation effect of the disulfide bond-containing compound, preferably, the charging sequence of the preparation method is as follows:
1) dissolving an initiator in a first pore forming agent to form an initiator solution;
2) performing copolymerization reaction on the DVS, the TVS, the first pore-forming agent, the second pore-forming agent and the initiator solution;
wherein the ratio of the weight of the first pore-forming agent in the step 1) to the total amount of the pore-forming agent in the step 2) is 1: 2.5-5, wherein the weight ratio of the first pore-forming agent to the second pore-forming agent in the step 2) is 1: 1-6.
In the present invention, the reaction conditions of the copolymerization reaction can be selected within a wide range, but in order to further improve the specific surface area and permeability of the resulting organo-silica gel hybrid thiophilic monolith, thereby improving the enrichment and separation effects of disulfide bond-containing compounds, it is preferable that the copolymerization reaction satisfies the following conditions: irradiating for 0.1-4h under the ultraviolet light with the wavelength of 254-365 nm.
In the above embodiment, the concentration of the initiator in the initiator solution can be selected within a wide range, but in order to further improve the specific surface area and permeability of the resulting organo-silica gel hybrid thiophilic monolith and thereby improve the enrichment and separation effects on the disulfide bond-containing compound, it is preferable that the concentration of the initiator in the initiator solution is 0.3 to 0.5 mol/L.
In the present invention, the reaction vessel for the double bond polymerization reaction may be a glass vessel conventional in the art, such as a centrifuge tube, a test tube and a chromatographic column, but in order to obtain an organic-inorganic hybrid thiophilic monolithic material having more excellent properties, it is preferable that the polymerization reaction is performed in a centrifuge tube or a capillary tube; wherein, the organic-silica gel hybrid thiophilic monolithic material obtained in the centrifuge tube can be crushed and filled into a chromatographic column; more preferably, the polymerization reaction is carried out in a capillary tube, whereby the organic-silica gel hybrid thiophilic monolithic material in the capillary tube is in a block shape, and then unreacted substances are removed by leaching to obtain an organic-silica gel hybrid thiophilic monolithic material with uniform pore size; therefore, the organic-silica gel hybrid thiophilic monolithic material exists in the capillary, the complicated filling process can be reduced, and the organic-silica gel hybrid thiophilic chromatographic material is better combined with a chromatographic column, so that the organic-silica gel hybrid thiophilic monolithic material can be directly applied to enrichment and separation of disulfide compounds in a mixed sample.
On the basis of the above contents, in order to further improve the binding force between the organic-silica gel hybrid thiophilic chromatographic material and the chromatographic column, preferably, the inner wall of the capillary is derived with carbon-carbon double bonds; therefore, the divinyl sulfone can react with double bond groups on the inner wall of the capillary, and meanwhile, the polymerization reaction is carried out simultaneously, so that the prepared organic-silica gel hybrid thiophilic chromatographic material can be more stably fixed in the capillary, and therefore, the organic-silica gel hybrid thiophilic chromatographic material can be repeatedly used in the capillary.
In the above embodiment, the compound specifically provided for the carbon-carbon double bond may be selected within a wide range, but preferably, the carbon-carbon double bond is provided by vinyltrimethoxysilane or 3- (methacrylamide) propyltrimethoxysilane in consideration of the ease of deriving the carbon-carbon double bond from the inner wall of the capillary. The specific operation is as follows: and (3) placing the cleaned capillary tube in silane containing carbon-carbon double bonds for contact reaction for 8-12h at 40-95 ℃ in the presence of an organic solvent. Of course, the organic solvent can be selected from multiple kinds, such as one or more selected from acetonitrile, acetone, methanol and ethanol. Among them, the amounts of vinyltrimethoxysilane and the organic solvent used may be selected within a wide range, but it is preferable that the amount of the organic solvent used is 0.5 to 10 parts by weight with respect to 1 part by weight of the vinyltrimethoxysilane in consideration of cost and solvent effect of the organic solvent.
In the above embodiment, the specification of the capillary may be selected within a wide range, but in view of the conventional specification of the column in the related art, it is preferable that the inner diameter of the capillary is 25 μm, 75 μm, 100 μm, 150 μm, or 250 μm.
In the above technical solution, the divinyl sulfone (DVS), the Tetravinylsilane (TVS) and the porogen may be mixed in various ways, such as stirring, shaking, and ultrasonic, which can be implemented in the present invention, and in the following embodiments, a vortex oscillator may be used to fully shake the mixture, and the ultrasonic treatment may be performed for 20 minutes.
In the present invention, in order to further remove unreacted materials, a porogen, etc., preferably, after the copolymerization reaction is completed, the preparation method further comprises extracting or rinsing the reaction product by at least one of methanol, ethanol, acetone, and n-hexane.
The invention also provides an organic-silica gel hybrid thiophilic monolithic material, which is characterized in that the organic-silica gel hybrid thiophilic monolithic material is prepared by the preparation method.
The invention further provides application of the organic-silica gel hybrid thiophilic monolithic material in enrichment and separation of specificity of compounds containing disulfide bonds.
The present invention will be described in detail below by way of examples. M below represents mol/L, and PEG represents polyethylene glycol.
Preparation example 1
Washing the capillary tube with NaOH (0.1M), water, HCl (0.1M), water and methanol for 30min in sequence; then drying the washed capillary tube (the inner diameter is 75 mu m) for 12h by using nitrogen; then placing the dried capillary tube into a mixed solution of Vinyltrimethoxysilane (VTMS) and methanol (volume ratio of VTMS/methanol is 1: 1) for contact reaction at 50 ℃ for 12.0 h; after the reaction is finished, the capillary tube is flushed by methanol and dried by nitrogen for 12 hours to obtain the capillary tube with the inner wall derived double bonds. The diameter of the capillary is one of 25 μm, 75 μm, 100 μm, 150 μm and 250 μm; or multiple are prepared simultaneously.
Example 1
Preparing a thiophilic porous material by adopting a photoinitiation method:
1) photoinitiator (2): 1.0252g (4mmol) of benzoin dimethyl ether is taken and dissolved in 10mL of n-propanol (8g) to prepare a 0.4mol/L benzoin dimethyl ether solution;
2) taking 24.6mg TVS, 53.4mg DVS, 48mg PEG200, 8.0mg n-propanol and 25 mu L benzoin dimethyl ether solution, fully dissolving by using a vortex oscillator, and carrying out ultrasonic treatment for 20 minutes to obtain uniformly mixed polymerization liquid;
3) pressing the obtained polymerization solution into the capillary tube with double bonds derived from the inner wall prepared in preparation example 1 by using nitrogen, sealing two ends of the capillary tube by using a silica gel sheet, and irradiating for 1.0h under an ultraviolet lamp of 365nm to prepare the organic-silica gel hybrid thiophilic chromatographic material;
4) and connecting the prepared organic-silica gel hybrid thiophilic chromatographic material on a high-pressure liquid chromatography pump, and washing by using methanol as a mobile phase to remove unreacted polymerization monomers, pore-forming agents, photoinitiators and the like to obtain the organic-silica gel hybrid thiophilic chromatographic material.
Example 2
1) Photoinitiator (2): dissolving benzoin dimethyl ether in n-propanol to prepare 0.3mol/L benzoin dimethyl ether solution;
2) mixing TVS, DVS, benzoin dimethyl ether solution and pore-forming agent according to the weight ratio of 1: 1: 0.6: 1.8, and ultrasonically mixing for 20 minutes to obtain uniformly mixed polymerization liquid; wherein the pore-foaming agent is prepared from the following components in a weight ratio of 1: 1.25 of n-propanol and polyethylene glycol 200;
3) the polymerization solution obtained above was pressed into the capillary tube with double bonds derived from the inner wall prepared in preparation example 1 with nitrogen, both ends of the capillary tube were sealed with a silicone sheet, and subjected to polymerization reaction of DVS and TVS by irradiation with ultraviolet light (wavelength 254nm) for 0.1 h;
4) and connecting the prepared organic-silica gel hybrid thiophilic chromatographic material on a high-pressure liquid chromatography pump, and washing by using methanol as a mobile phase to remove unreacted polymerization monomers, pore-forming agents, photoinitiators and the like to obtain the organic-silica gel hybrid thiophilic chromatographic material.
Example 3
1) Photoinitiator (2): dissolving benzoin dimethyl ether in n-propanol to prepare 0.3mol/L benzoin dimethyl ether solution;
2) mixing TVS, DVS, benzoin dimethyl ether solution and pore-forming agent according to the weight ratio of 1: 3: 1.5: 6 for 20 minutes to obtain uniformly mixed polymerization liquid; wherein the pore-foaming agent is prepared from the following components in a weight ratio of 1: 1, n-propanol and polyethylene glycol 200;
3) the polymerization solution obtained above was pressed into the capillary tube with double bonds derived from the inner wall prepared in preparation example 1 with nitrogen, both ends of the capillary tube were sealed with a silicone sheet, and subjected to DVS and TVS polymerization by irradiation with ultraviolet light (wavelength 254nm) for 4 hours;
4) and connecting the prepared organic-silica gel hybrid thiophilic chromatographic material on a high-pressure liquid chromatography pump, and washing by using methanol as a mobile phase to remove unreacted polymerization monomers, pore-forming agents, photoinitiators and the like to obtain the organic-silica gel hybrid thiophilic chromatographic material.
Detection example 1
The appearance of the thiophilic porous material prepared in example 1 is observed by a scanning electron microscope, and the detection result is shown in fig. 2. as shown in fig. 2, the thiophilic porous material with uniform pore size distribution and a highly cross-linked structure can be obtained by a photo-initiation method, and the thiophilic porous material is firmly combined with the inner wall of the capillary.
Detection example 2
The infrared spectrum detection of the organic-silica gel hybrid thiophilic monolithic material prepared in example 1 is performed by using a fourier infrared method, and the result is shown in fig. 3, and the specific analysis of the organic-inorganic thiophilic monolithic material Poly (DVS-co-TVS) is as follows, in combination with the graph and related knowledge: a) infrared spectrum of tetravinylsilane, characteristic absorption peak of double bond (2923 cm)-1) (ii) a b) Infrared spectrum of divinyl sulfone, characteristic absorption peak of sulfone group (1296 cm)-1，1126cm-1) (ii) a c) YP is an infrared spectrogram of an organic-inorganic hybrid thiophilic monolithic material Poly (DVS-co-TVS), and the infrared spectrogram can obviously observe that all the organic-silica gel hybrid Poly (DVS-co-TVS) monolithic materials prepared by a photoinitiation method have a characteristic absorption peak of sulfone group (1296 cm)-1，1126cm-1) Characteristic absorption Peak of double bond (2923 cm)-1) To illustrate the successful polymerization of DVS and TVS, the organo-silica hybrid thiophilic monolithic materials can be prepared using a photo-initiated method.
Detection example 3
Elemental analysis of the organo-silica gel hybrid thiophilic monolithic material prepared in example 1 was performed by EDX (energy dispersive x-ray spectroscopy), and the results are shown in fig. 4; the graph clearly shows that the organic-silica gel hybrid thiophilic monolithic materials prepared by the light-induced method all contain obvious S elements, and the successful preparation of the organic-silica gel hybrid thiophilic monolithic materials is proved again.
Detection example 4
Thermal stability analysis was performed on the thiophilic porous material prepared in example 1 by TGA (thermogravimetric analysis), and the results correspond to fig. 5, respectively; as can be clearly seen from FIG. 5, the first thermal decomposition temperature of the organic-silica gel hybrid thiophilic chromatographic material prepared by the photoinitiation method is about 225 ℃, which proves that the thiophilic porous material has good thermal stability.
Detection example 5
The porous material for thiophilic chromatography prepared in example 1 was subjected to nitrogen adsorption method detection to detect the pore diameter and specific surface area, and the results are shown in table 1, which shows that the porous material for thiophilic chromatography prepared in the present invention has a large specific surface area.
TABLE 1
| Thiophilic monolithic materials | Specific surface area (m)2/g) | Average pore diameter (μm) |
| Example 1 | 6.973 | 0.15 |
Detection example 6
The micro-column liquid phase detection condition adopts a Trisep2000 separation system, is provided with a two-gradient elution device and is provided with a 1.0 mu L quantitative ring. The capillary thiophilic porous material of 15cm length prepared in example 1 was used as a chromatographic column, methanol and acetonitrile were used as mobile phases, respectively, the flow rate was gradually increased, the pressure after the column of the microcolumn liquid phase was recorded, and the permeability coefficient was calculated according to the darcy formula, and the results are shown in table 2. As can be seen from Table 2, the sulfur-philic porous material prepared by the present invention has strong permeability.
TABLE 2
| Mobile phase | Post back pressure MPa | Permeability coefficient 10-14m2 |
| Methanol | 19.0 | 0.675 |
| Acetonitrile | 15.7 | 7.8 |
Preparation example 2 (application example 1 preparation of Medium reagent)
1) Preparation of 0.02mg/mL Standard solution of bis (4-hydroxyphenyl) disulfide (2S-OH): 1.0mg of 2S-OH was dissolved in 50.0mL of 0.5M aqueous sodium sulfate solution (containing 5% by weight of acetonitrile) at 25 ℃ to prepare 0.02mg/mL of a 2S-OH standard solution.
2) Preparation of 0.02mg/mL Standard solution of bis (4-hydroxyphenyl) methane (2-OH): 1.0mg of bis (4-hydroxyphenyl) methane was dissolved in 50mL of 0.5M aqueous sodium sulfate solution (containing 5% by weight of acetonitrile) at 25 ℃ to prepare 0.02mg/mL of a 2-OH standard solution.
3) Preparation of 0.02mg/mL of a 2S-OH and 2-OH mixed solution: 1.0mg of 2S-OH and 2-OH was dissolved in 50.0mL of 0.5M aqueous sodium sulfate solution (containing 5% by weight of acetonitrile) at 25 ℃ to prepare a 0.02mg/mL mixed solution of 2S-OH and 2-OH.
4) Preparing a sample solution: 0.716g of disodium hydrogenphosphate and 0.355g of sodium sulfate were dissolved in 45.0mL of distilled water at 25 ℃, then adjusted to pH 6.2 with 1M aqueous citric acid solution, and then made to volume of 50.0mL to obtain a sample.
5) Preparation of eluent: 0.716g of disodium hydrogenphosphate was added to 45mL of distilled water at 25 ℃ and then adjusted to pH 8.5 with 1M aqueous citric acid solution, followed by volume adjustment to 50mL to obtain an eluent.
Preparation example 3 (application example 2 preparation of Medium reagent)
1) Preparing a sample solution: 0.716g of disodium hydrogenphosphate and 1.8638g of potassium chloride were dissolved in 45.0mL of distilled water at 25 ℃, then adjusted to pH 6.2 with 1M aqueous citric acid solution, and then made to volume of 50.0mL to obtain a sample.
2) Preparation of eluent: 0.716g of disodium hydrogenphosphate was added to 45mL of distilled water at 25 ℃ and then adjusted to pH 6.2 with 1M aqueous citric acid solution, followed by volume adjustment to 50.0mL to obtain an eluent.
3) Preparation of electrophoretic separation buffer: 1.950g of disodium hydrogenphosphate, 0.731g of sodium chloride and 7.210g of sodium dodecyl sulfate were dissolved in 240.0mL of distilled water, and the solution was adjusted to pH 8.5 with 1M of an aqueous citric acid solution, and the volume was adjusted to 250.0mL to prepare an electrophoretic separation buffer solution.
A standard solution was prepared in the same manner as in preparation example 2, except that 0.5mol of an aqueous sodium sulfate solution was changed to 0.5mol of an aqueous potassium chloride solution.
Application example 1
1) The micro-column liquid phase detection condition, Trisep2000 separation system, is equipped with two gradient elution devices, 1.0 μ L quantitative ring, the detection wavelength is 214 nm. A30 cm long sulfur-philic porous material prepared in example 1 was used as a chromatographic column. The sample solution and the eluent are prepared in preparation example 2; flow rate of mobile phase: 4.0. mu.L/min.
2) 0.1mg/mL of bis (4-hydroxyphenyl) disulfide (2S-OH) standard solution, 0.1mg/mL of bis (4-hydroxyphenyl) methane (2-OH) standard solution, 0.1mg/mL of a mixed solution of 2S-OH and 2-OH in preparation example 2 above, 1.0uL were sequentially subjected to detection under the conditions of the above-mentioned micro-column liquid phase detection.
As a result, it was found that under the same conditions, 2-OH could not be specifically retained by the monolith under high-concentration salt conditions, while 2S-OH could be specifically retained. After the flow phase exchange, the 2S-OH can be smoothly eluted. The result shows that Poly (DVS-co-TVS) in the organic-silica gel hybrid thiophilic monolithic material has good specific enrichment effect on the compound containing the disulfide bond.
Application example 2
And (3) enriching 2S-OH by using a thiophilic porous material and carrying out capillary electrophoresis detection.
1) The sample solution and the eluent were prepared by the method in preparation example 3.
2) 1.0mL of the sample solution was injected into the thiophilic chromatography material of example 1 and equilibrated for 60min, followed by 50. mu.L of 1mg/mL of 2S-OH standard solution for immobilization for 30 min;
3) injecting 20 mu L of the sample solution into the thiophilic chromatographic material to wash and remove the non-immobilized 2S-OH, and injecting 6 mu L of eluent into the thiophilic chromatographic material to elute the 2S-OH to prepare 2S-OH eluent;
4) by capillary electrophoresis (P/ACE)tmMDQ, beckmann, usa) to perform electrophoresis detection on the 2S-OH eluate under the specific detection conditions: in a fused silica capillary having an inner diameter of 75.0 μm (total length of 56.5cm, effective length of 50 cm); the infrared detection wavelength was 214nm and the sample size was 5 s.times.0.5 psi.
The detection results are shown in fig. 6, and in fig. 6: curve a is the chromatogram of the background buffer solution, curve b is the chromatogram of the eluent, curve c is the chromatogram of the mixed standard solution of 0.02mg/mL 2S-OH and 2-OH which is not adsorbed by the thiophilic porous material, curve d is the chromatogram of the standard solution of 0.02mg/mL 2-OH, curve e is the chromatogram of the standard solution of 0.02mg/mL 2S-OH, and curve f is the chromatogram of the component eluted after the enrichment of the material.
Under the same conditions, 2-OH cannot be specifically retained by the thiophilic porous material under the condition of high-concentration salt, and 2S-OH can be specifically retained. After the flow phase exchange, the 2S-OH can be smoothly eluted. The result shows that the sulfur-philic porous material has good specific enrichment effect on the compound containing the disulfide bond.
As a result, the organo-silica gel hybrid thiophilic monolithic material prepared in example 1 was found to be enriched by 1.55 times for 2S-OH and to have a static retention capacity of 0.0029 mg/g. Therefore, the sulfur-philic porous material has better enrichment and separation effects on the compounds containing disulfide bonds.
The detection results of the products of examples 2-3 were consistent with those of the product of example 1, as determined by the above-described detection examples and application examples.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (8)
1. A preparation method of an organic-silica gel hybrid thiophilic monolithic material is characterized by comprising the following steps: in the presence of light and an initiator, divinyl sulfone DVS and tetravinyl silane TVS are subjected to copolymerization reaction in a pore-foaming agent to prepare an organic-silica gel hybrid thiophilic monolithic material Poly (DVS-co-TVS); wherein the weight ratio of the TVS to the DVS to the pore-foaming agent is 1: 1-3: 2.1-7.4;
the weight ratio of the TVS to the initiator is 1: 0.04-0.15; wherein the porogenic agent comprises a first porogenic agent and a second porogenic agent, the first porogenic agent is selected from at least one of n-propanol, isopropanol and dimethyl sulfoxide, and the second porogenic agent is selected from at least one of polyethylene glycol 200, polyethylene glycol 300, polyethylene glycol 400, polyethylene glycol 600 and diethylene glycol diethyl ether;
the initiator is selected from at least one of benzoin, benzoin dimethyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin butyl ether; the preparation method comprises the following material adding sequence:
1) dissolving the initiator in the first pore-foaming agent to form an initiator solution;
2) carrying out copolymerization reaction on the DVS, the TVS, the first pore-foaming agent, the second pore-foaming agent and an initiator solution;
wherein the ratio of the weight of the first pore-forming agent in the step 1) to the total amount of the pore-forming agent in the step 2) is 1: 2.5-5, wherein the weight ratio of the first pore-foaming agent to the second pore-foaming agent in the step 2) is 1: 1-6.
2. The production method according to claim 1, wherein the copolymerization reaction satisfies the following condition: irradiating for 0.1-4h under the ultraviolet light with the wavelength of 254-365 nm.
3. The production method according to claim 1, wherein the concentration of the initiator in the initiator solution is 0.3 to 0.5 mol/L.
4. The method of claim 1, wherein the copolymerization reaction is performed in a centrifuge tube or a capillary tube.
5. The method of claim 4, wherein the inner wall of the capillary is derivatized with carbon-carbon double bonds.
6. The method of claim 5, wherein the carbon-carbon double bond is provided by vinyltrimethoxysilane or 3- (methacrylamide) propyltrimethoxysilane.
7. The production method according to claim 6, wherein the capillary has an inner diameter of 25 μm, 75 μm, 100 μm, 150 μm, or 250 μm.
8. The preparation method according to claim 1, wherein the preparation method further comprises extracting or rinsing the reaction product by at least one of methanol, ethanol, acetone, and n-hexane after the copolymerization reaction is finished.
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| CN103861555A (en) * | 2013-12-10 | 2014-06-18 | 天津大学 | Preparation method of multi-porous silica gel liquid chromatographic monolithic column |
| CN105542076A (en) * | 2016-01-28 | 2016-05-04 | 安徽师范大学 | Thiophilic porous material, and preparation method and application thereof |
| CN105566671A (en) * | 2014-10-13 | 2016-05-11 | 中国科学院大连化学物理研究所 | Preparation method of organic-inorganic hybrid porous integral material |
| CN107106932A (en) * | 2015-01-15 | 2017-08-29 | 戴安公司 | Chromatographic material, its preparation method and its purposes with improved pH stability |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2006272190A (en) * | 2005-03-29 | 2006-10-12 | Jsr Corp | Transparent hygroscopic composition, molding, film and its production method |
| CN103861555A (en) * | 2013-12-10 | 2014-06-18 | 天津大学 | Preparation method of multi-porous silica gel liquid chromatographic monolithic column |
| CN105566671A (en) * | 2014-10-13 | 2016-05-11 | 中国科学院大连化学物理研究所 | Preparation method of organic-inorganic hybrid porous integral material |
| CN107106932A (en) * | 2015-01-15 | 2017-08-29 | 戴安公司 | Chromatographic material, its preparation method and its purposes with improved pH stability |
| CN105542076A (en) * | 2016-01-28 | 2016-05-04 | 安徽师范大学 | Thiophilic porous material, and preparation method and application thereof |
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