CN108329428B - Thiophilic porous material and preparation method and application thereof - Google Patents
Thiophilic porous material and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J20/282—Porous sorbents
- B01J20/285—Porous sorbents based on polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F228/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur
- C08F228/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur by a bond to sulfur
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a chromatographic material, and discloses a thiophilic porous material, a preparation method and application thereof, wherein the preparation method comprises the following steps: mixing divinyl sulfone (DVS), 2,4,6, 8-tetramethyl-2, 4,6, 8-tetravinylcyclotetrasiloxane (TMTVS) and a pore-foaming agent, and carrying out polymerization reaction on the DVS and the TMTVS under the photo-initiation or thermal initiation condition; wherein, under the photoinitiation condition, the mixture also comprises a photoinitiator; under the thermal initiation condition, the mixture also comprises a thermal initiator and glacial acetic acid. The reaction process is easier to control, and the obtained sulfur-philic porous material has larger specific surface area and permeability, and better enrichment and separation effects on compounds containing disulfide bonds, and moreover, the sulfur-philic porous material has a 3D framework structure, strong mechanical properties and good stability.
Description
Technical Field
The invention relates to a chromatographic material, in particular to a thiophilic porous material and a preparation method and application thereof.
Background
Chromatographic separation has wide application in medicine, chemistry, life science, environmental science and other fields. The chromatographic column is the core of the chromatographic system and is the key to achieving efficient separation. Therefore, the research and development of the novel chromatographic separation medium have important theoretical and practical significance.
The chromatographic monolithic materials are divided into three major internal classes, namely organic polymer monolithic materials, inorganic monolithic materials and organic-inorganic hybrid monolithic materials. The organic polymer integral material has the advantages of simple preparation, wide pH application range, abundant functional monomers and the like, but the swelling property of the organic solvent reduces the mechanical stability and the separation column effect. The inorganic silica gel column material has the advantages of high mechanical strength, good chemical stability, high column efficiency and the like, but the preparation process of the silica gel monolithic column material is complicated, the surface is easy to crack, a plunger needs to be burnt, and the pH application range is low, so that the development of the silica gel monolithic column material is severely limited. The organic-inorganic hybrid monolithic material is prepared by bonding organic matters and inorganic matters through covalent reaction, and has the advantages of organic polymeric monolithic column materials and inorganic monolithic materials. Thus, organic-inorganic hybrid monolithic materials have received a high degree of attention in recent years.
The existing thiophilic chromatographic material has obvious defects, such as unstable mechanical property, incapability of bearing high pressure, easy loss of functional groups, poor repeatability and the like. The capillary tube integral material is used as a fourth generation separation medium, so that a complicated filling process is omitted, a special penetrating hole and a skeleton hole in the capillary tube integral material provide a stable macroporous channel for liquid flowing, a slow diffusion mass transfer process is replaced by a convection mass transfer process, and mass transfer resistance is obviously reduced. Therefore, the invention provides the preparation method of the thiophilic capillary monolithic column which is stable in mechanical property, large in specific surface area, large in pore size and better in enrichment effect.
Disclosure of Invention
The invention aims to provide a thiophilic porous material and a preparation method and application thereof, the thiophilic porous material is prepared by polymerizing divinyl sulfone and 2,4,6, 8-tetramethyl-2, 4,6, 8-tetravinylcyclotetrasiloxane, the reaction process is easier to control, and the obtained thiophilic porous material has larger specific surface area and permeability and better enrichment and separation effects on compounds containing disulfide bonds, and the thiophilic porous material has a 3D framework structure, strong mechanical property and good stability.
In order to achieve the above object, the present invention provides a method for preparing a thiophilic porous material, comprising: mixing divinyl sulfone (DVS), 2,4,6, 8-tetramethyl-2, 4,6, 8-tetravinylcyclotetrasiloxane (TMTVS) and a pore-foaming agent, and carrying out polymerization reaction on the DVS and the TMTVS under the photo-initiation or thermal initiation condition; wherein, under the photoinitiation condition, the mixture also comprises a photoinitiator; under the thermal initiation condition, the mixture also comprises a thermal initiator and glacial acetic acid.
The invention also provides a sulfur-philic porous material prepared by the preparation method.
Furthermore, the present invention provides the use of a thiophilic porous material according to the preamble for the specific enrichment and isolation of disulfide bond containing compounds.
According to the technical scheme, the thiophilic porous material prepared by polymerizing divinyl sulfone and 2,4,6, 8-tetramethyl-2, 4,6, 8-tetravinylcyclotetrasiloxane can be used for obtaining the target thiophilic porous material under a photo-initiation condition or a thermal initiation condition, the reaction process is easier to control, and the obtained thiophilic porous material has larger specific surface area and permeability and better enrichment and separation effects on compounds containing disulfide bonds, and not only does the thiophilic porous material have a 3D framework structure, strong mechanical properties and good stability.
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 a thiophilic porous material Poly (DVS-co-TMTVS);
FIG. 2 is a scanning electron micrograph of a thiophilic porous material Poly (DVS-co-TMTVS) in example 1: a) 1300 times of scanning electron microscope image, b) 3500 times of scanning electron microscope image, c) 6000 times of scanning electron microscope image;
FIG. 3 is a scanning electron micrograph of a thiophilic porous material Poly (DVS-co-TMTVS) in example 4: a) 1300 times of scanning electron microscope image, b) 3500 times of scanning electron microscope image, c) 6000 times of scanning electron microscope image;
FIG. 4 is a Fourier transform infrared spectrum of a sulfur-philic porous material Poly (DVS-co-TMTVS) prepared in example 1;
FIG. 5 is a Fourier transform infrared spectrum of a sulfur-philic porous material Poly (DVS-co-TMTVS) prepared in example 4;
FIG. 6 is an energy dispersive X-ray spectroscopy chart of a thiophilic porous material Poly (DVS-co-TMTVS) prepared in example 1;
FIG. 7 is an energy dispersive X-ray spectroscopy chart of a thiophilic porous material Poly (DVS-co-TMTVS) prepared in example 4;
FIG. 8 is a thermogravimetric analysis curve of the thiophilic porous material Poly (DVS-co-TMTVS) prepared in example 1;
FIG. 9 is a thermogravimetric analysis curve of the thiophilic porous material Poly (DVS-co-TMTVS) prepared in example 4;
FIG. 10 is an electrophoretogram of the sulfur-philic porous material Poly (DVS-co-TMTVS) prepared in example 1 for specific separation and enrichment of disulfide bond-containing compounds;
FIG. 11 is an electrophoretogram of the sulfur-philic porous material Poly (DVS-co-TMTVS) prepared in example 4 for specific separation and enrichment of disulfide bond-containing compounds.
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 a thiophilic porous material, which comprises the following steps: mixing divinyl sulfone (DVS), 2,4,6, 8-tetramethyl-2, 4,6, 8-tetravinylcyclotetrasiloxane (TMTVS) and a pore-foaming agent, and carrying out polymerization reaction on the DVS and the TMTVS under the photo-initiation or thermal initiation condition; wherein, under the photoinitiation condition, the mixture also comprises a photoinitiator; under the thermal initiation condition, the mixture also comprises a thermal initiator and glacial acetic acid.
According to the technical scheme, the thiophilic porous material prepared by polymerizing divinyl sulfone and 2,4,6, 8-tetramethyl-2, 4,6, 8-tetravinylcyclotetrasiloxane can be used for obtaining the target thiophilic porous material under a photo-initiation condition or a thermal initiation condition, the reaction process is easier to control, and the obtained thiophilic porous material has larger specific surface area and permeability and better enrichment and separation effects on compounds containing disulfide bonds, and not only does the thiophilic porous material have a 3D framework structure, strong mechanical properties and good stability.
In a preferred embodiment of the present invention, in order to make the reaction process easier to control, and the obtained thiophilic porous material has a large specific surface area and permeability, and has a good enrichment and separation effect on compounds containing disulfide bonds, moreover, the thiophilic porous material has a 3D framework structure, strong mechanical properties, and good stability, and preferably, the weight ratio of DVS, TMTVS and porogen is 1-3: 1: 3-7.3.
In a preferred embodiment of the present invention, in order to make the reaction process easier to control, and the obtained thiophilic porous material has large specific surface area and permeability, and has good enrichment and separation effects on disulfide bond-containing compounds, moreover, the thiophilic porous material has a 3D framework structure, and has strong mechanical properties and good stability, preferably, when the polymerization reaction is carried out under photoinitiation conditions, the mixture contains, in parts by weight: relative to 1 weight portion of TMTVS, the usage amount of DVS is 1 to 3 portions, the usage amount of photoinitiator is 0.0001 to 0.002 portion, and the usage amount of pore-forming agent is 3 to 7.3 portions.
In a preferred embodiment of the present invention, in order to make the reaction process easier to control, and the obtained thiophilic porous material has large specific surface area and permeability, and has good enrichment and separation effects on disulfide bond-containing compounds, moreover, the thiophilic porous material has a 3D framework structure, and has strong mechanical properties and good stability, preferably, when the polymerization reaction is carried out under thermal initiation conditions, the mixture contains, in parts by weight: relative to 1 weight part of TMTVS, the usage amount of DVS is 1-3 parts, the usage amount of thermal initiator is 0.05-0.19 part, the usage amount of glacial acetic acid is 0.93-3.0 parts, and the usage amount of pore-forming agent is 2-6.3 parts.
In a preferred embodiment of the present invention, in order to make the reaction process easier to control and obtain a thiophilic porous material with large specific surface area and permeability and good enrichment and separation effects on disulfide bond-containing compounds, the thiophilic porous material has a 3D framework structure, strong mechanical properties and good stability, and preferably, the step of performing the polymerization reaction under photoinitiation conditions comprises irradiating the mixture with ultraviolet light for 0.1-4 h.
In a preferred embodiment of the invention, in order to make the reaction process easier to control, and the obtained sulfur-philic porous material has larger specific surface area and permeability, and has better enrichment and separation effects on compounds containing disulfide bonds, moreover, the sulfur-philic porous material has a 3D framework structure, strong mechanical properties and good stability, and preferably, the wavelength of ultraviolet light is 254-365 nm.
In a preferred embodiment of the present invention, in order to make the reaction process easier to control and obtain a thiophilic porous material with large specific surface area and permeability and better enrichment and separation effects on disulfide bond-containing compounds, the thiophilic porous material has a 3D framework structure, strong mechanical properties and good stability, and preferably, the step of performing the polymerization reaction under thermal initiation conditions comprises reacting the mixture at 60-90 ℃ for 2-15 h.
In a preferred embodiment of the present invention, the polymerization is preferably carried out in a centrifuge tube. The thus obtained thiophilic porous material may be added to a chromatographic column by crushing.
In a preferred embodiment of the invention, the polymerization is preferably carried out in a capillary tube in order to reduce the cumbersome packing procedure and to allow better binding of the thiophilic porous material to the chromatographic column.
Of course, the type of capillary may be selected according to the actual requirements, for example, in a preferred embodiment of the invention, the diameter of the capillary may be selected from one of 25 μm, 75 μm, 100 μm, 150 μm and 250 μm.
The reaction conditions and the amounts of the raw materials are as described above, except that the vessel used in the polymerization reaction is only changed to a capillary tube with double bonds derived from the inner wall, so that divinyl sulfone can react with the double bond groups on the inner wall of the capillary tube, and the polymerization reaction is carried out at the same time, so that the prepared sulfur-philic porous material is fixed in the capillary tube, and the sulfur-philic porous material can be reused in the capillary tube.
Wherein the capillary tube of the inner wall derived double bond can be selected conventionally in the art, in a preferred embodiment, the capillary tube of the inner wall derived double bond is prepared by the following method: and (3) putting the cleaned capillary tube in vinyltrimethoxysilane in the presence of an organic solvent for contact reaction. Of course, the organic solvent herein may be of a type conventionally employed in the art, for example, in a preferred embodiment of the present invention, the organic solvent may be selected from one or more of acetonitrile, acetone, methanol and ethanol.
The amounts of vinyltrimethoxysilane and organic solvent used herein can, of course, be selected according to the actual circumstances, for example, in a preferred embodiment of the present invention, the second organic solvent is used in an amount of 0.5 to 10 parts by weight relative to 1 part by weight of the vinyltrimethoxysilane.
The contact reaction conditions are not limited, and in order to further increase the reaction rate, in a more preferred embodiment of the present invention, the contact reaction may be carried out at 40 to 95 ℃ for 8 to 12 hours. And then, washing with methanol to remove unreacted substances, and drying the pretreated capillary tube by using nitrogen gas, thereby successfully preparing the capillary tube with the double bonds derived from the inner wall.
In a preferred embodiment of the present invention, in order to enhance the effect of separating the disulfide bond-containing compound, it is preferable that the production method further comprises a step of washing the polymer obtained after the polymerization reaction with a solvent.
Of course, the selection of the solvent, which is preferably one or more of methanol, ethanol and acetonitrile, can be flexibly adjusted by those skilled in the art as long as the unreacted materials, the porogen, and the like are removed.
In a preferred embodiment of the present invention, in order to make the reaction process easier to control, and the obtained thiophilic porous material has a larger specific surface area and permeability, and has better enrichment and separation effects on compounds containing disulfide bonds, moreover, the thiophilic porous material has a 3D framework structure, and has strong mechanical properties and good stability, preferably, the porogen consists of a first porogen and a second porogen together; wherein the first pore-foaming agent is one or more of normal propyl alcohol, isopropanol and dimethyl sulfoxide; the second pore-foaming agent is one or more of polyethylene glycol 200, polyethylene glycol 300, polyethylene glycol 400, polyethylene glycol 600 and diethylene glycol diethyl ether.
Wherein, polyethylene glycol 200, polyethylene glycol 300, polyethylene glycol 400, polyethylene glycol 600 are polyethylene glycols of different specifications, wherein corresponding 200, 300, 400, 600 refer to the average molecular weight of the polyethylene glycol.
In a preferred embodiment of the present invention, in order to make the reaction process easier to control, and the obtained thiophilic porous material has a large specific surface area and permeability, and has a good enrichment and separation effect on compounds containing disulfide bonds, moreover, the thiophilic porous material has a 3D framework structure, strong mechanical properties, and good stability, and preferably, the weight ratio of the first pore-forming agent to the second pore-forming agent is 1: 0.3-4.
In a preferred embodiment of the present invention, in order to make the reaction process easier to control, and the obtained thiophilic porous material has a large specific surface area and permeability, and has a good enrichment and separation effect on compounds containing disulfide bonds, moreover, the thiophilic porous material has a 3D framework structure, and has strong mechanical properties and good stability, and preferably, the photoinitiator is one or more of benzoin, benzoin dimethyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin butyl ether.
In a preferred embodiment of the present invention, in order to make the reaction process easier to control, and the obtained thiophilic porous material has larger specific surface area and permeability, and better enrichment and separation effects on compounds containing disulfide bonds, moreover, the thiophilic porous material has a 3D framework structure, strong mechanical properties, and good stability, preferably, in the preparation method, the photoinitiator is dissolved in the first pore agent to form a photoinitiator solution, and then the photoinitiator solution is added to the mixture to be subjected to polymerization reaction.
In a preferred embodiment of the present invention, in order to make the reaction process easier to control, and the obtained thiophilic porous material has a large specific surface area and permeability, and has a good enrichment and separation effect on compounds containing disulfide bonds, moreover, the thiophilic porous material has a 3D framework structure, and is strong in mechanical properties and good in stability, and preferably, the total concentration of benzoin, benzoin dimethyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin butyl ether in the photoinitiator solution is 0.3-0.5 mol/L.
In a preferred embodiment of the present invention, in order to make the reaction process easier to control, and the resulting thiophilic porous material has a large specific surface area and permeability, and has a good enrichment and separation effect on disulfide bond-containing compounds, not only the thiophilic porous material has a 3D framework structure, and is strong in mechanical properties and good in stability, but also it is further preferred that the photoinitiator solution is used in an amount of 1 to 3 parts per 1 part by weight of the TMTVS.
In a preferred embodiment of the present invention, in order to make the reaction process easier to control, and the obtained sulfur-philic porous material has a larger specific surface area and permeability, and has a better enrichment and separation effect on compounds containing disulfide bonds, moreover, the sulfur-philic porous material has a 3D framework structure, strong mechanical properties, and good stability, and preferably, the total concentration of benzoin, benzoin dimethyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin butyl ether in the solution is 0.4 mol/L.
In a preferred embodiment of the present invention, in order to make the reaction process easier to control, and the resulting thiophilic porous material has a large specific surface area and permeability, and has a good enrichment and separation effect on disulfide bond-containing compounds, and furthermore, the thiophilic porous material has a 3D framework structure, strong mechanical properties, and good stability, preferably, the thermal initiator is one or more of benzoyl peroxide, azobisisobutyronitrile ((ABIN)), azobisisoheptonitrile, azobisisobutyramidine hydrochloride, and azobisdiisopropylamidine oxazoline hydrochloride, and more preferably, the thermal initiator is Azobisisobutyronitrile (ABIN).
In the above technical solution, the divinyl sulfone (DVS), 2,4,6, 8-tetramethyl-2, 4,6, 8-tetravinylcyclotetrasiloxane (TMTVS) and porogen may be mixed in various ways, such as stirring, shaking, and ultrasound, to implement the present invention, and in the following embodiments, the mixing is performed by fully shaking with a vortex shaker and performing ultrasound for 20 minutes.
The invention also provides a sulfur-philic porous material prepared by the preparation method.
According to the technical scheme, the thiophilic porous material prepared by polymerizing divinyl sulfone and 2,4,6, 8-tetramethyl-2, 4,6, 8-tetravinylcyclotetrasiloxane can be used for obtaining the target thiophilic porous material under a photo-initiation condition or a thermal initiation condition, the reaction process is easier to control, and the obtained thiophilic porous material has larger specific surface area and permeability and better enrichment and separation effects on compounds containing disulfide bonds, and not only does the thiophilic porous material have a 3D framework structure, strong mechanical properties and good stability.
Furthermore, the present invention provides the use of a thiophilic porous material according to the preamble for the specific enrichment and isolation of disulfide bond containing compounds.
According to the technical scheme, the thiophilic porous material prepared by polymerizing divinyl sulfone and 2,4,6, 8-tetramethyl-2, 4,6, 8-tetravinylcyclotetrasiloxane can be used for obtaining the target thiophilic porous material under a photo-initiation condition or a thermal initiation condition, the reaction process is easier to control, and the obtained thiophilic porous material has larger specific surface area and permeability and better enrichment and separation effects on compounds containing disulfide bonds, and not only does the thiophilic porous material have a 3D framework structure, strong mechanical properties and good stability.
The present invention will be described in detail below by way of examples, in which all reagents are conventional commercially available analytical reagents for chemical analysis.
Preparation example 1
Pre-treatment of the inner wall of the capillary with derivatized double bonds: the pretreatment process comprises the following steps: the first step is to use 0.1mol/L NaOH and H respectively2O (ultrapure water), 0.1mol/L HCl, H2The capillary was purged with O (ultra pure water) and methanol for 30 minutes and then blown dry with nitrogen. The second step is that a uniformly mixed solution prepared by methanol and vinyl trimethoxy silane (v/v-1/1) is injected into a capillary tube and reacts for 12 hours in a constant temperature environment of 50 ℃; washing with methanol to remove unreacted substances, and blow-drying the pretreated capillary tube with nitrogen to obtain a capillary tube with double bonds derived from the inner wall; 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 solution: 1.0252g of benzoin dimethyl ether is taken and dissolved in 10mL of n-propanol to prepare a 0.4mol/L solution;
(2) taking 15 μ L (14.5mg) of TMTVS, 25 μ L (32.1mg) of DVS, 52.5 μ L (64.4mg) of PEG400 and 25 μ L (23.7mg) of the photoinitiator solution prepared in the step (1), fully dissolving the solution by using a vortex oscillator, and carrying out ultrasonic treatment for 20 minutes to obtain a uniformly mixed polymerization solution;
(3) pressing the obtained polymerization solution into a capillary tube with double bonds derived from the inner wall in preparation example 1 by using nitrogen, sealing two ends of the capillary tube by using a silica gel sheet, and irradiating for 1.25h under an ultraviolet lamp of 365nm to prepare a thiophilic porous material;
(4) and connecting the prepared thiophilic porous material on a high-pressure liquid chromatography pump, and washing by taking methanol as a mobile phase to remove unreacted polymerization monomers, pore-forming agents, photoinitiators and the like to obtain the thiophilic porous material.
Example 2
A method for preparing a thiophilic porous material, comprising:
(1) photoinitiator solution: dissolving benzoin dimethyl ether in n-propanol to prepare a 0.3mol/L solution;
(2) ultrasonically mixing 1 part of TMTVS, 1 part of DVS, 1 part of photoinitiator solution in the step (1) and 3 parts of pore-forming agent for 20 minutes by weight to obtain uniformly mixed polymerization liquid; wherein the pore-foaming agent consists of n-propanol and polyethylene glycol 400 together, and the weight and dosage ratio of the n-propanol to the polyethylene glycol 400 is 1: 0.3;
(3) the polymerization solution obtained above was pressed into a capillary tube with double bonds derived from the inner wall of preparation example 1 with nitrogen, both ends of the capillary tube were sealed with a silica gel sheet, and irradiated with ultraviolet light (wavelength 254nm) for 4 hours to perform a polymerization reaction of DVS and TMTVS;
(4) and connecting the prepared thiophilic porous material on a high-pressure liquid chromatography pump, and washing by taking methanol as a mobile phase to remove unreacted polymerization monomers, pore-forming agents, photoinitiators and the like to obtain the thiophilic porous material.
Example 3
A method for preparing a thiophilic porous material, comprising:
(1) photoinitiator solution: dissolving benzoin dimethyl ether in n-propanol to prepare a 0.5mol/L solution;
(2) ultrasonically mixing 1 part of TMTVS, 3 parts of DVS, 3 parts of the photoinitiator solution in the step (1) and 7.3 parts of a pore-foaming agent for 20 minutes by weight to obtain uniformly mixed polymerization liquid; wherein the pore-foaming agent consists of n-propanol and polyethylene glycol 400 together, and the weight and dosage ratio of the n-propanol to the polyethylene glycol 400 is 1: 4;
(3) the polymerization solution obtained above was pressed into a capillary tube with double bonds derived from the inner wall of preparation example 1 with nitrogen, both ends of the capillary tube were sealed with a silica gel sheet, and irradiated with ultraviolet light (wavelength 300nm) for 0.1 hour to perform polymerization of DVS and TMTVS;
(4) and connecting the prepared thiophilic porous material on a high-pressure liquid chromatography pump, and washing by taking methanol as a mobile phase to remove unreacted polymerization monomers, pore-forming agents, photoinitiators and the like to obtain the thiophilic porous material.
Example 4
Preparing a thiophilic porous material by adopting a thermal initiation method:
(1) mu.L (31.1mg) of TMTVS, 47. mu.L (54.9mg) of DVS, 28. mu.L (29.8mg) of HAc, 4.0mg of AIBN as an initiator, 40. mu.L (33.5mg) of NPA (n-propanol) and 85. mu.L (76mg) of DEGDE (diethylene glycol diethyl ether) were placed in a 2.5mL centrifuge tube and vortexed and degassed by sonication to give a well-mixed solution;
(2) injecting the solution into the pretreated capillary tube in the preparation example 1, and reacting for 12 hours in a water bath kettle at 75 ℃ to prepare a thiophilic porous material;
(3) and (3) washing the prepared thiophilic porous material with methanol to remove unreacted substances, and finally preparing the thiophilic porous material.
Example 5
Preparing a thiophilic porous material by adopting a thermal initiation method:
(1) putting 1 part of TMTVS, 1 part of DVS, 0.05 part of thermal initiator, 0.93 part of glacial acetic acid and 2 parts of pore-forming agent into a centrifugal tube by weight parts, and performing vortex oscillation and ultrasonic degassing to obtain a uniformly mixed solution; the pore-foaming agent consists of n-propanol (NPA) and diethylene glycol diethyl ether (DEGDE) together, wherein the weight ratio of n-propanol to diethylene glycol diethyl ether is 1: 0.3;
(2) injecting the solution into the pretreated capillary tube in the preparation example 1, and reacting for 15h in a water bath kettle at 90 ℃ to prepare a thiophilic porous material;
(3) and (3) washing the prepared thiophilic porous material with methanol to remove unreacted substances, and finally preparing the thiophilic porous material.
Example 6
Preparing a thiophilic porous material by adopting a thermal initiation method:
(1) putting 1 part of TMTVS, 3 parts of DVS, 0.19 part of thermal initiator, 3.0 parts of glacial acetic acid and 6.3 parts of pore-forming agent into a centrifugal tube by weight parts, and performing vortex oscillation and ultrasonic degassing to obtain a uniformly mixed solution; the pore-foaming agent consists of n-propanol and diethylene glycol diethyl ether, wherein the weight ratio of n-propanol to diethylene glycol diethyl ether is 1: 4;
(2) injecting the solution into the pretreated capillary tube in the preparation example 1, and reacting for 2h in a water bath kettle at 60 ℃ to prepare a thiophilic porous material;
(3) and (3) washing the prepared thiophilic porous material with methanol to remove unreacted substances, and finally preparing the thiophilic porous material.
Detection example 1
The appearance of the thiophilic porous materials prepared in the examples 1 and 4 is observed by adopting a scanning electron microscope. The detection results correspond to fig. 2 and fig. 3, respectively, and as shown in fig. 2 and fig. 3, a thiophilic porous material with uniform pore size distribution and a highly cross-linked structure can be obtained by using either a photo-initiation method or a thermal initiation method, and the material is firmly combined with the inner wall of the capillary.
Detection example 2
Infrared spectrum detection is carried out on the thiophilic porous material prepared by photo-initiation in the example 1 by adopting a Fourier infrared method, and the result is shown in a figure 4 and can be seen: a) infrared spectrogram of 2,4,6, 8-tetramethyl-2, 4,6, 8-tetravinylcyclotetrasiloxane and characteristic absorption peak of double bond (2957 cm)-1) (ii) a b) Infrared spectrum of divinyl sulfone, characteristic absorption peak of sulfone group (1311 cm)-1，1126cm-1) (ii) a c) An infrared spectrogram of a thiophilic porous material Poly (DVS-co-TMTVS), wherein a YP curve in the graph can obviously observe that the thiophilic porous material prepared by a photoinitiation method has a characteristic absorption peak of sulfone group (1311 cm)-1，1126cm-1) Characteristic absorption Peak of double bond (2957 cm)-1) Illustrating the successful polymerization of DVS and TMTVS, the reaction principle is shown in fig. 1, and the thiophilic porous material can be prepared by a thermal initiation method.
When the thiophilic porous materials prepared in examples 2 and 3 were examined in the same manner, characteristic peaks shown in fig. 4 appeared, and it can be seen that thiophilic porous materials were also prepared in examples 2 and 3.
Detection example 3
The infrared spectrum detection of the thiophilic porous material prepared by thermal initiation in example 4 is carried out by a Fourier infrared method, and the result is shown in figure 5, which shows that: a) infrared spectrogram of 2,4,6, 8-tetramethyl-2, 4,6, 8-tetravinylcyclotetrasiloxane and characteristic absorption peak of double bond (2943 cm)-1) (ii) a b) Divinyl sulfone Infrared Spectrum, characteristic absorption Peak of sulfone group (1307 cm)-1，1136cm-1) (ii) a c) Infrared spectrogram of thiophilic porous material Poly (DVS-co-TMTVS), YP curve can be obviously observed by a method of thermal initiationThe prepared sulfur-philic porous material has a characteristic absorption peak of sulfuryl (1307 cm)-1，1136cm-1) Characteristic absorption Peak of double bond (2943 cm)-1) Illustrating the successful polymerization of DVS and TMTVS, the reaction principle is shown in fig. 1, and the thiophilic porous material can be prepared by a thermal initiation method.
When the thiophilic porous materials prepared in examples 5 and 6 were examined in the same manner, characteristic peaks shown in fig. 5 appeared, and it can be seen that thiophilic porous materials were also prepared in examples 2 and 3.
Detection example 4
The sulfur-philic porous materials prepared in examples 1 and 4 were subjected to elemental analysis using EDX (energy dispersive x-ray spectroscopy), and the results thereof corresponded to fig. 6 and 7, respectively. It can be clearly seen from fig. 6 and 7 that the sulfur-philic porous materials prepared by the two methods both contain obvious S element, and the successful preparation of the sulfur-philic porous material is proved again.
Detection example 5
The results of thermal stability analysis of the thiophilic porous materials prepared in examples 1 and 4 by TGA (thermogravimetric analysis) correspond to fig. 8 and 9, respectively. It can be clearly seen from fig. 8 and 9 that the first thermal decomposition temperature of the porous thiophilic material prepared by the two methods is about 250 ℃, which proves that the porous thiophilic material has good thermal stability.
Detection example 6
The porous materials of the thiophilic chromatography prepared in example 1 and example 4 were tested for pore size and specific surface area by nitrogen adsorption method, and the results are shown in table 1, which shows that the porous materials of the thiophilic chromatography prepared in the present invention have a large specific surface area.
TABLE 1
Detection example 7
The micro-column liquid phase detection condition, Trisep2000 separation system, is equipped with two gradient elution devices, 1.0 μ L quantitative ring. The capillary thiophilic porous material of 15cm length prepared in example 1 and example 4, respectively, was used as a chromatographic column, water was used as a mobile phase, 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, with the results 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
Preparation example 2: preparation of solutions to be tested in the application examples
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% 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% 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% 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: preparation of the solutions used in the application examples
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 and example 4 was used as a chromatographic column. The sample liquid and the eluent are prepared by the method 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, and 0.1mg/mL of a mixed solution of 2S-OH and 2-OH (1.0 uL) in preparation example 2 were sequentially subjected to detection under the conditions of the above-mentioned microcolumn 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-TMTVS) in the sulfur-philic porous material has good specific enrichment effect on the compounds containing disulfide bonds.
Application example 2
And (3) enriching 2S-OH by using a thiophilic porous material and carrying out capillary electrophoresis detection.
The sample solution and the eluent were prepared by the method in preparation example 3.
2) Injecting 1.0mL of the sample solution into the thiophilic chromatographic material to balance for 60min, and then injecting 50 mu L of 1mg/mL of 2S-OH standard solution to immobilize 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) performs electrophoresis detection on 2S-OH eluate under conditions of 75.0 μm inner diameter fused silica capillary (total length of 56.5cm, effective length of 50cm), infrared detection wavelength of 214nm, and sample introduction amount of 5S × 0.5.5 psi.
The results of the detection of the thiophilic porous materials in application examples 1 and 4 correspond to fig. 10 and 11, respectively. In fig. 10 and 11: curve a is the electrophoretogram of the background buffer solution, curve b is the electrophoretogram of the eluent, curve c is the electrophoretogram 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 electrophoretogram of the standard solution of 0.02mg/mL 2-OH, curve e is the electrophoretogram of the standard solution of 0.02mg/mL 2S-OH, curve f is the electrophoretogram of the fraction 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, it was found that the sulfur-philic porous material 1 prepared in example 1 was enriched in 2S-OH by a factor of 3.33, and had a static retention capacity of 6.68mg/g, and the sulfur-philic porous material 1 prepared in example 4 was enriched in 2.25, and had a static retention capacity of 15.1 mg/g.
It can be seen that the sulfur-philic porous material has better enrichment and separation effects on compounds containing disulfide bonds.
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 (14)
1. A method for preparing a thiophilic porous material, comprising:
mixing divinyl sulfone (DVS), 2,4,6, 8-tetramethyl-2, 4,6, 8-tetravinylcyclotetrasiloxane (TMTVS) and a pore-foaming agent, and carrying out polymerization reaction on the DVS and the TMTVS under the photo-initiation or thermal initiation condition;
wherein, under the photoinitiation condition, the mixture also comprises a photoinitiator; under the condition of thermal initiation, the mixture also comprises a thermal initiator and glacial acetic acid; wherein the weight ratio of DVS, TMTVS and pore-foaming agent is 1-3: 1: 3-7.3; wherein, when the polymerization reaction is carried out under the photoinitiation condition, the weight portions of the mixture are as follows: relative to 1 weight part of TMTVS, the usage amount of DVS is 1 to 3 parts, the usage amount of photoinitiator is 0.0001 to 0.002 part, and the usage amount of pore-forming agent is 3 to 7.3 parts;
or, when the polymerization reaction is carried out under the thermal initiation condition, the following components in the mixture are calculated according to the weight portion: relative to 1 weight part of TMTVS, the usage amount of DVS is 1-3 parts, the usage amount of thermal initiator is 0.05-0.19 part, the usage amount of glacial acetic acid is 0.93-3.0 parts, and the usage amount of pore-forming agent is 2-6.3 parts;
wherein the pore-foaming agent consists of a first pore-foaming agent and a second pore-foaming agent; wherein the first pore-foaming agent is one or more of normal propyl alcohol, isopropanol and dimethyl sulfoxide; the second pore-foaming agent is one or more of polyethylene glycol 200, polyethylene glycol 300, polyethylene glycol 400, polyethylene glycol 600 and diethylene glycol diethyl ether; wherein the weight ratio of the first pore-foaming agent to the second pore-foaming agent is 1: 0.3-4.
2. The method of claim 1, wherein the step of polymerizing under photoinitiated conditions comprises irradiating the mixture with ultraviolet light for 0.1 to 4 hours.
3. The method according to claim 2, wherein the wavelength of the ultraviolet light is 254-365 nm; alternatively, the step of carrying out the polymerization under thermally initiated conditions comprises reacting the mixture at 60-90 ℃ for 2-15 h.
4. The method of claim 2, wherein the polymerization reaction is performed in a centrifuge tube and/or a capillary tube.
5. The production method according to claim 4, wherein an inner diameter of the capillary is one of 25 μm, 75 μm, 100 μm, 150 μm, and 250 μm.
6. The production method according to claim 5, wherein the capillary is a capillary whose inner wall is derivatized with a double bond.
7. The production method according to claim 4, further comprising a step of washing the polymer obtained after the polymerization with a solvent.
8. The production method according to claim 7, wherein the solvent is one or more of methanol, ethanol, and acetonitrile.
9. The method of claim 1, wherein the photoinitiator is one or more of benzoin, benzoin dimethyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin butyl ether.
10. The production method according to claim 9, wherein, in the production method: the photoinitiator is dissolved in the first porogen to form a photoinitiator solution, and the photoinitiator solution is added to the mixture to be polymerized.
11. The method according to claim 10, wherein the total concentration of benzoin, benzoin dimethyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin butyl ether in the photoinitiator solution is 0.3 to 0.5 mol/L.
12. The preparation method of claim 11, wherein the photoinitiator solution is used in an amount of 1 to 3 parts relative to 1 part by weight of the TMTVS;
or the thermal initiator is one or more of benzoyl peroxide, Azobisisobutyronitrile (ABIN), azobisisoheptonitrile, azobisisobutyramidine hydrochloride and azobisdiisopropylamidine oxazoline hydrochloride.
13. The sulfur-philic porous material produced by the production method according to any one of claims 1 to 12.
14. Use of a thiophilic porous material according to claim 13 for specific enrichment and isolation of disulfide bond containing compounds.
Priority Applications (1)
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| CN104707568A (en) * | 2013-12-13 | 2015-06-17 | 中国科学院大连化学物理研究所 | Porous monolithic material for chromatographic separation, and preparation method and application thereof |
| 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 |
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| CN104707568A (en) * | 2013-12-13 | 2015-06-17 | 中国科学院大连化学物理研究所 | Porous monolithic material for chromatographic separation, 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 |
| 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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