CN102872613A - Preparation method of organic-inorganic hybridization monolithic column - Google Patents
Preparation method of organic-inorganic hybridization monolithic column Download PDFInfo
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- CN102872613A CN102872613A CN2012103555099A CN201210355509A CN102872613A CN 102872613 A CN102872613 A CN 102872613A CN 2012103555099 A CN2012103555099 A CN 2012103555099A CN 201210355509 A CN201210355509 A CN 201210355509A CN 102872613 A CN102872613 A CN 102872613A
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Abstract
The invention relates to a preparation method of an organic-inorganic hybridization monolithic column. According to the preparation method, a monolithic column framework with a sulfydryl group on the surface is formed through a silane coupling agent, and the 'click chemical reaction' between sulfydryl and a double bond is utilized at the same time, and a carbon double bond functional monomer containing terminal carbon is directly bonded to the surface of the monolithic column, thus, a step of chemically modifying again in a later period can be avoided; the preparation method provided by the invention is simple, and has good reproducibility, high universality, and a wide application range, and brings benefit for developing more hybridization monolithic columns with different functional groups.
Description
Technical field
The present invention relates to the preparation method of integral post, particularly a kind of preparation method of organic-inorganic hybrid integral post.
Background technology
Integral post is whole stationary phase bed layer formed continuously by the method for in-situ polymerization, porous.Integral post has micron-sized skeleton and through hole simultaneously, and nano level mesopore, therefore, compares with traditional filled-type chromatographic column, has good penetrability, mass transfer rate advantages of higher.In addition, the easy regulation and control that realize its pore structure, specific area, surface nature in the integral post preparation process.These advantages so that integral post as a kind of novel separating medium, play an increasingly important role in various fields such as chemistry, medicine, food, environmental protection, biochemistry and industry preparations.
According to the kind of material, integral post can be divided into two types of Organic Polymer Monolithic Columns and silica matrix integral post.The Organic Polymer Monolithic Columns preparation is simple, good biocompatibility, but a distinct disadvantage is arranged, be exactly that swelling or contraction easily occur in some solvent, cause the change of overall structure performance.Monolithic silica column is stable under the organic solvent condition, has preferably mechanical stability, post effect advantages of higher, but in dry and roasting process, very easily produce cracking and shrinkage phenomenon, and usually need the cost certain hour monolithic silica column to be modified to introduce functional group, whole preparation process more complicated.The hybrid integral post is to grow up on the basis of monolithic silica column, and is stable under the organic solvent condition, and has preferably mechanical stability, can avoid cracking and shrinkage phenomenon simultaneously.Therefore, the preparation and application of organic-inorganic hybrid integral post become the another study hotspot of chromatography.
The preparation method of organic-inorganic hybrid integral post mainly adopts in reactant to add to be had chromatogram and keeps the functionalization trimethoxy of group or the sol-gel processing of triethoxy monomer.At present, reported the organic-inorganic hybrid integral post that has synthesized many difference in functionality groups, and such as long chain hydrocarbon groups, phenyl, amino, sulfonate radical etc. (" Electrophoresis " magazine, the 26th volume, 2935(2005); " Journal of Chromatography A " magazine, the 1121st volume, 92(2006); " Journal of Chromatography A " magazine, the 1046th volume, 255(2004); Journal of Chromatography A " magazine, the 1217th volume, 3547(2004)), application succeeds under the plurality of color spectral models such as high efficiency liquid phase, microtrabeculae liquid phase, Capillary Electrophoresis, pressurization electrochromatography.
In recent years, many seminars attempt one after another function monomer modified that multi-band has the hybrid integral post of difference in functionality group to develop more in hybrid integral post surface, and obtain certain breakthrough.The people such as Zou (" Analytical Chemistry " magazine the 81st volume, 3529(2009)) developed the technology of " one kettle way " preparation hybrid integral post, namely in reactant, add tetramethoxy-silicane, vinyltrimethoxy silane, function monomer dodecyl dimethyl pi-allyl bromination ammonium and initator azodiisobutyronitrile, at first reaction 12h forms the surface with the skeleton of vinyl functional group under 40 ° of C, then under 60 ° of C, react 12h, utilize the radical reaction between two keys that function monomer is bonded to formation surface, integral post surface with the hybrid integral post of long carbochain, and be successfully applied to the analysis of the enzymolysis product of bovine serum albumin enzymolysis product and mouse liver extract.The people such as Yao (" Talanta " magazine, the 91st volume, 52(2012)) by " click chemistry (click reaction) " between sulfydryl-two keys reaction modification is carried out on the vinyl hybrid integral post surface that has prepared, synthesized the hybrid integral post with long chain hydrocarbon groups and sulfonate radical bifunctional group, and carried out the chromatographic performance evaluation with substituted benzene, 5 kinds of aromatic amine materials, prove that this integral post has hydrophobic and retention mechanism ion-exchange simultaneously.
Yet, the preparation method of above-mentioned organic-inorganic hybrid integral post still faces commercial functionalization trimethoxy or the triethoxy monomer that chromatogram keeps group that have, and the kind of function monomer that contains sulfydryl is few, needs artificial complex functionality monomer, and step is complicated; Needed for two steps added thermal response 24h, the long bottleneck that waits of manufacturing cycle.
Summary of the invention
For the deficiency that exists in the background technology, the invention provides a kind of preparation method of organic-inorganic hybrid integral post, its concrete scheme is as follows:
A kind of preparation method of organic-inorganic hybrid integral post is characterized in that: form the surface with the integral post skeleton of mercapto groups with silane coupling reagent; Utilize simultaneously " click chemistry reaction " between sulfydryl-two keys, when monolithic silica column forms, will contain terminal carbon-carbon double bond function monomer and be bonded directly to the integral post surface.
Concrete steps are as follows:
1) with silane coupler
The pore-foaming agent that reaches reacting dose is hydrolyzed in formic acid or acetic acid solution, obtains solution 1;
2) initator of the reacting dose that the function monomer of terminal carbon-carbon double bonds and generation " click chemistry reaction " is required joins in the solution 1, mixes and makes pre-polymerization liquid;
3) made pre-polymerization liquid of upper step is inserted through in the pretreated capillary, sealed at both ends, in 20 ℃～80 ℃ temperature ranges, make its reaction form the homogeneous cylinder, wash reacted capillary with organic solvent, the reaction reagent of flush away remnants, and get final product.
As preference:
Described pore-foaming agent is polyethylene glycol, PEO or polyacrylamide.
Described initator is azodiisobutyronitrile, azobisisobutryamide chloride.
Described organic solvent is methyl alcohol, ethanol, isopropyl alcohol, acetone, acetonitrile, dimethyl formamide or dimethyl sulfoxide (DMSO).
Beneficial effect of the present invention is presented as:
1) preparation process of the present invention is simple, and manufacturing cycle is short;
2) integral post favorable reproducibility, the universality of the present invention preparation are strong, applied widely, help to develop the hybrid integral post that multi-band more has the difference in functionality group.
Description of drawings
Fig. 1: the inventive method prepares the schematic diagram of organic-inorganic hybrid integral post;
The ζ of the integral post of Fig. 2: embodiment 1 preparation-electromotive force phenogram;
The ion exchange chromatographic evaluation figure of the integral post of Fig. 3: embodiment 1 preparation;
The IR Characterization figure of the integral post of Fig. 4: embodiment 2 preparations;
The hydrophilic Interaction Chromatography evaluation map of the integral post of Fig. 5: embodiment 2 preparations;
Wherein, 1: toluene; 2: thymidine; : 3: uridine; 4: adenosine; 5: cytidine; 6: guanosine;
Fig. 6: gained organic-inorganic hybrid integral rod structure schematic diagram of the present invention.
The specific embodiment
Following examples further specify content of the present invention, but should not be construed as limitation of the present invention.Without departing from the spirit and substance of the case in the present invention, modification or replacement to the inventive method, step or condition are done all belong to scope of the present invention.
This example is take tetramethoxy-silicane and 3-sulfydryl propyl trimethoxy silicane as silane coupler, and MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride is function monomer, preparation MATE-hybrid integral post.
1. preparation integral post
Take by weighing 185mg tetramethoxy-silicane, 15mg3-sulfydryl propyl trimethoxy silicane, 25mg polyethylene glycol, 500mg 0.01M acetic acid in centrifuge tube, hydrolysis fully.Then, add 16mg MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and 1mg azodiisobutyronitrile, mix, make pre-polymerization liquid.Pre-polymerization liquid is inserted through in the pretreated capillary, sealed at both ends, under 40 ℃ of temperature, make its reaction form the homogeneous cylinder, with the reacted capillary of washed with methanol, the reaction reagent of flush away remnants, and get final product.
2. product detects
1) the integral post ζ of preparation-electromotive force characterizes as shown in Figure 2.
2) ion exchange chromatographic evaluation: take above-mentioned MATE-hybrid integral post as splitter (30cmx75 μ m i.d.), investigate under the different salinity retention behaviors of 4 kinds of organic acids on MATE-hybrid integral post such as ortho-aminobenzoic acid, benzoic acid, m-Nitrobenzoic Acid, salicylic acid.Mobile phase is that volume ratio is the acetonitrile/sodium hydrogen phosphate aqueous solution (salinity be respectively 10,15,20,25mM) of 20:80, linear velocity 0.8mm/s, and it is 230nm that ultraviolet detects wavelength;
As shown in Figure 3, increase with salinity, 4 kinds of organic acids reservations weaken.
Embodiment 2
This example is take tetramethoxy-silicane and 3-sulfydryl propyl trimethoxy silicane as silane coupler, and acrylamide is function monomer, preparation AA-hybrid integral post.
1, preparation integral post
Take by weighing 185mg tetramethoxy-silicane, 15mg 3-sulfydryl propyl trimethoxy silicane, 40mg polyethylene glycol, 500mg 0.01M acetic acid in centrifuge tube, hydrolysis fully.Then, add 6mg acrylamide and 1mg azodiisobutyronitrile, mix, make pre-polymerization liquid.Pre-polymerization liquid is inserted through in the pretreated capillary, sealed at both ends, in 45 ℃ of temperature ranges, make its reaction form the homogeneous cylinder, wash reacted capillary with acetonitrile, the reaction reagent of flush away remnants, and get final product.
2. product detects
1) IR Characterization of the integral post of preparation as shown in Figure 4.
2) hydrophilic Interaction Chromatography evaluation: take above-mentioned AA-hybrid integral post as splitter (30cmx75 μ m i.d.), investigate under the different ethane nitrile content conditions retention behaviors of 5 kinds of nucleosides on the AA integral post such as adenosine, thymidine, guanosine, cytidine, uridine.Mobile phase is the acetonitrile/water solution (V:V is respectively 85:15,90:10,95:5) of certain volume ratio, linear velocity 0.8mm/s, and it is 256nm that ultraviolet detects wavelength;
As shown in Figure 5, increase with ethane nitrile content, 5 kinds of nucleosides keep enhancing.
Wherein, 1: toluene; 2: thymidine; : 3: uridine; 4: adenosine; 5: cytidine; 6: guanosine.
Embodiment 3
Take by weighing 190mg tetramethoxy-silicane, 10mg 3-sulfydryl propyl trimethoxy silicane, 30mg polyethylene glycol, 500mg 0.01M formic acid in centrifuge tube, hydrolysis fully.Then, add 10mg MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and 1mg azodiisobutyronitrile, mix, make pre-polymerization liquid.Pre-polymerization liquid is inserted through in the pretreated capillary, sealed at both ends, in 35 ℃ of temperature ranges, make its reaction form the homogeneous cylinder, with the reacted capillary of washed with methanol, the reaction reagent of flush away remnants, and get final product.
Embodiment 4
Take by weighing 180mg tetramethoxy-silicane, 20mg 3-sulfydryl propyl trimethoxy silicane, 35mg polyethylene glycol, 500mg 0.01M formic acid in centrifuge tube, hydrolysis fully.Then, add 21mg MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and 1mg azodiisobutyronitrile, mix, make pre-polymerization liquid.Pre-polymerization liquid is inserted through in the pretreated capillary, sealed at both ends, in 25 ℃ of temperature ranges, make its reaction form the homogeneous cylinder, with the reacted capillary of washed with methanol, the reaction reagent of flush away remnants, and get final product.
Take by weighing 170mg tetramethoxy-silicane, 30mg 3-sulfydryl propyl trimethoxy silicane, 33mg PEO, 500mg 0.01M acetic acid in centrifuge tube, hydrolysis fully.Then, add 15mg acrylamide and 1mg azobisisobutryamide chloride, mix, make pre-polymerization liquid.Pre-polymerization liquid is inserted through in the pretreated capillary, sealed at both ends, in 60 ℃ of temperature ranges, make its reaction form the homogeneous cylinder, wash reacted capillary with acetonitrile, the reaction reagent of flush away remnants, and get final product.
Take by weighing 160mg tetramethoxy-silicane, 40mg 3-sulfydryl propyl trimethoxy silicane, 27mg PEO, 500mg 0.01M acetic acid in centrifuge tube, hydrolysis fully.Then, add 25mg acrylamide and 1mg azobisisobutryamide chloride, mix, make pre-polymerization liquid.Pre-polymerization liquid is inserted through in the pretreated capillary, sealed at both ends, in 80 ℃ of temperature ranges, make its reaction form the homogeneous cylinder, wash reacted capillary with acetonitrile, the reaction reagent of flush away remnants, and get final product.
Claims (5)
1. the preparation method of an organic-inorganic hybrid integral post is characterized in that: form the surface with the integral post skeleton of mercapto groups with silane coupling reagent; Utilize simultaneously " click chemistry reaction " between sulfydryl-two keys, when monolithic silica column forms, will contain terminal carbon-carbon double bond function monomer and be bonded directly to the integral post surface.
2. preparation method's as claimed in claim 1 concrete steps, it is characterized in that: step is as follows:
1) with silane coupler
The pore-foaming agent that reaches reacting dose is hydrolyzed in formic acid or acetic acid solution, obtains solution 1;
2) initator of the reacting dose that the function monomer of terminal carbon-carbon double bonds and generation " click chemistry reaction " is required joins in the solution 1, mixes and makes pre-polymerization liquid;
3) made pre-polymerization liquid of upper step is inserted through in the pretreated capillary, sealed at both ends, in 20 ℃～80 ℃ temperature ranges, make its reaction form the homogeneous cylinder, wash reacted capillary with organic solvent, the reaction reagent of flush away remnants, and get final product.
3. such as the preparation method of claim 1 and 2 described organic-inorganic hybrid integral posts, it is characterized in that: described pore-foaming agent is polyethylene glycol, PEO or polyacrylamide.
4. such as the preparation method of claim 1 and 2 described organic-inorganic hybrid integral posts, it is characterized in that: described initator is azodiisobutyronitrile, azobisisobutryamide chloride.
5. such as the preparation method of claim 1 and 2 described organic-inorganic hybrid integral posts, it is characterized in that: described organic solvent is methyl alcohol, ethanol, isopropyl alcohol, acetone, acetonitrile, dimethyl formamide or dimethyl sulfoxide (DMSO).
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104084178A (en) * | 2014-06-23 | 2014-10-08 | 广西师范大学 | Stationary phase of POSS hybrid capillary monolithic column, and preparation method thereof |
| CN105664529A (en) * | 2016-01-15 | 2016-06-15 | 福州大学 | Amphoteric hydrophilic organic-silica gel hybrid monolithic column and preparation method thereof |
| CN106000349A (en) * | 2016-05-06 | 2016-10-12 | 东华大学 | Preparation method of acetylated polyvinyl alcohol monolithic column |
| CN106669229A (en) * | 2016-11-30 | 2017-05-17 | 洛阳理工学院 | Preparation method of C12 bonded organic-inorganic hybrid monolithic column and application of preparation method |
| CN107213877A (en) * | 2017-05-15 | 2017-09-29 | 华南师范大学 | A kind of synthetic method of the trace mesoporous material to bisphenol-A with high selectivity |
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2012
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Non-Patent Citations (1)
| Title |
|---|
| KEYI WANG, YINGZHUANG CHEN, HUIHUI YANG, YI LI, LIHUA NIE, SHOUZ: "《Modification of VTMS hybrid monolith via thiol-ene click chemistry for 》", 《TALANTA》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104084178A (en) * | 2014-06-23 | 2014-10-08 | 广西师范大学 | Stationary phase of POSS hybrid capillary monolithic column, and preparation method thereof |
| CN104084178B (en) * | 2014-06-23 | 2016-11-23 | 广西师范大学 | POSS hybridization capillary tube monolithic column fixes phase and preparation method thereof |
| CN105664529A (en) * | 2016-01-15 | 2016-06-15 | 福州大学 | Amphoteric hydrophilic organic-silica gel hybrid monolithic column and preparation method thereof |
| CN106000349A (en) * | 2016-05-06 | 2016-10-12 | 东华大学 | Preparation method of acetylated polyvinyl alcohol monolithic column |
| CN106669229A (en) * | 2016-11-30 | 2017-05-17 | 洛阳理工学院 | Preparation method of C12 bonded organic-inorganic hybrid monolithic column and application of preparation method |
| CN107213877A (en) * | 2017-05-15 | 2017-09-29 | 华南师范大学 | A kind of synthetic method of the trace mesoporous material to bisphenol-A with high selectivity |
| CN107213877B (en) * | 2017-05-15 | 2020-06-12 | 华南师范大学 | Synthetic method of imprinted mesoporous material with high selectivity to bisphenol A |
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