CN102872613B - Preparation method of organic-inorganic hybridization monolithic column - Google Patents
Preparation method of organic-inorganic hybridization monolithic column Download PDFInfo
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- CN102872613B CN102872613B CN201210355509.9A CN201210355509A CN102872613B CN 102872613 B CN102872613 B CN 102872613B CN 201210355509 A CN201210355509 A CN 201210355509A CN 102872613 B CN102872613 B CN 102872613B
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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, in integral post preparation process, easily realize the regulation and control to its pore structure, specific area, surface nature.These advantages make integral post as a kind of novel separating medium, in various fields such as chemistry, medicine, food, environmental protection, biochemistry and industry preparations, play an increasingly important role.
According to the kind of material, integral post can be divided into two types of Organic Polymer Monolithic Columns and silica matrix integral post.Organic Polymer Monolithic Columns preparation is simple, good biocompatibility, but there is a distinct disadvantage, be exactly that swelling or contraction easily occur in some solvent, cause the change of overall structure performance.Monolithic silica column is stable under organic solvent condition, there is good mechanical stability, post effect advantages of higher, but in dry and roasting process, very easily produce cracking and shrinkage phenomenon, and conventionally need to spend certain hour monolithic silica column is modified to introduce functional group, whole preparation process more complicated.Hybrid integral post is to grow up on the basis of monolithic silica column, stable under organic solvent condition, and has good 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 to add in reactant has the chromatogram reservation 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, (< < Electrophoresis > > magazines such as long chain hydrocarbon groups, phenyl, amino, sulfonate radical, the 26th volume, 2935(2005); < < Journal of Chromatography A > > magazine, the 1121st volume, 92(2006); < < Jou rnal of Ch romatography A > > magazine, the 1046th volume, 255(2004); Journal ofChromatographyA > > magazine, the 1217th volume, 3547(2004)), the application that succeeds under the plurality of color spectral models such as high efficiency liquid phase, microtrabeculae liquid phase, Capillary Electrophoresis, pressurization electrochromatography.
In recent years, the numerous and confused trial of many seminars modified function monomer in hybrid integral post surface and had the hybrid integral post of difference in functionality group to develop more multi-band, and obtains certain breakthrough.The people such as Zou (< < Analytical Chemistry > > magazine the 81st volume, 3529(2009)) developed the technology that " one kettle way " prepares hybrid integral post, in reactant, add tetramethoxy-silicane, vinyltrimethoxy silane, function monomer dodecyl dimethyl pi-allyl bromination ammonium and initator azodiisobutyronitrile, first at 40 ℃, react 12h and form surface with the skeleton of vinyl functional group, then at 60 ℃, 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 the reaction) " reaction between sulfydryl-bis-keys, modification is carried out in the vinyl hybrid integral post surface having prepared, synthesized the hybrid integral post with long chain hydrocarbon groups and sulfonate radical bifunctional group, and with substituted benzene, 5 kinds of aromatic amine materials have carried out chromatographic performance evaluation, 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 retains group that have, and few containing the kind of the function monomer of sulfydryl, need artificial complex functionality monomer, step is complicated; Need two steps to add thermal response 24h, the long bottleneck that waits of manufacturing cycle.
Summary of the invention
For the deficiency existing in background technology, the invention provides a kind of preparation method of organic-inorganic hybrid integral post, its concrete scheme is as follows:
A preparation method for organic-inorganic hybrid integral post, is characterized in that: with silane coupling reagent, form surface with the integral post skeleton of mercapto groups; Utilize " click chemistry reaction " between sulfydryl-bis-keys simultaneously, when monolithic silica column forms, will be bonded directly to integral post surface containing end carbon-carbon double bond function monomer.
Concrete steps are as follows:
1) by silane coupler
and the pore-foaming agent of reacting dose is at formic acid
Or be hydrolyzed in acetic acid solution, obtain solution 1;
2) initator of the function monomer of end carbon-carbon double bonds and the required reacting dose of generation " click chemistry reaction " is joined in solution 1, mix and make pre-polymerization liquid;
3) the made pre-polymerization liquid of upper step is inserted through in pretreated capillary, sealed at both ends, in 20 ℃～80 ℃ temperature ranges, make its reaction form homogeneous cylinder, with organic solvent, rinse reacted capillary, wash away remaining reaction reagent, obtain.
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 that prepared by the present invention are strong, applied widely, contribute to develop the hybrid integral post that multi-band more has difference in functionality group.
Accompanying drawing explanation
Fig. 1: the inventive method is prepared the schematic diagram of organic-inorganic hybrid integral post;
ζ-electromotive force phenogram of the integral post of Fig. 2: embodiment 1 preparation;
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 illustrate 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, the modification that the inventive method, step or condition are done or replacement, all belong to scope of the present invention.
Embodiment 1
It is silane coupler that this example be take tetramethoxy-silicane and 3-sulfydryl propyl trimethoxy silicane, and MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride is function monomer, preparation MATE-hybrid integral post.
1. prepare integral post
Take 185mg tetramethoxy-silicane, 15mg 3-sulfydryl propyl trimethoxy silicane, 25mg polyethylene glycol, 500mg 0.01M acetic acid in centrifuge tube, hydrolysis completely.Then, add 16mg MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and 1mg azodiisobutyronitrile, mix, make pre-polymerization liquid.Pre-polymerization liquid is inserted through in pretreated capillary, sealed at both ends, at 40 ℃ of temperature, make its reaction form homogeneous cylinder, with the reacted capillary of washed with methanol, wash away remaining reaction reagent, obtain.
2. product detects
1) the integral post ζ preparing-electromotive force characterizes as shown in Figure 2.
2) ion exchange chromatographic evaluation: take above-mentioned MATE-hybrid integral post as splitter (30cm * 75 μ m i.d.), investigate under different salinity the retention behavior of 4 kinds of organic acids such as ortho-aminobenzoic acid, benzoic acid, m-Nitrobenzoic Acid, salicylic acid on MATE-hybrid integral post.Mobile phase is that volume ratio is 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, with salinity, increase, 4 kinds of organic acids reservations weaken.
Embodiment 2
It is silane coupler that this example be take tetramethoxy-silicane and 3-sulfydryl propyl trimethoxy silicane, and acrylamide is function monomer, preparation AA-hybrid integral post.
1, preparation integral post
Take 185mg tetramethoxy-silicane, 15mg 3-sulfydryl propyl trimethoxy silicane, 40mg polyethylene glycol, 500mg 0.01M acetic acid in centrifuge tube, hydrolysis completely.Then, add 6mg acrylamide and 1mg azodiisobutyronitrile, mix, make pre-polymerization liquid.Pre-polymerization liquid is inserted through in pretreated capillary, sealed at both ends, in 45 ℃ of temperature ranges, make its reaction form homogeneous cylinder, with acetonitrile, rinse reacted capillary, wash away remaining reaction reagent, obtain.
2. product detects
1) IR Characterization of the integral post of preparing as shown in Figure 4.
2) hydrophilic Interaction Chromatography evaluation: take above-mentioned AA-hybrid integral post as splitter (30cm * 75 μ m i.d.), investigate under different ethane nitrile content conditions the retention behavior of 5 kinds of nucleosides such as adenosine, thymidine, guanosine, cytidine, uridine in AA integral post.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, with ethane nitrile content, increase, 5 kinds of nucleosides retain enhancing.
Wherein, 1: toluene; 2: thymidine; 3: uridine; 4: adenosine; 5: cytidine; 6: guanosine.
Embodiment 3
Take 190mg tetramethoxy-silicane, 10mg 3-sulfydryl propyl trimethoxy silicane, 30mg polyethylene glycol, 500mg 0.01M formic acid in centrifuge tube, hydrolysis completely.Then, add 10mg MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and 1mg azodiisobutyronitrile, mix, make pre-polymerization liquid.Pre-polymerization liquid is inserted through in pretreated capillary, sealed at both ends, in 35 ℃ of temperature ranges, make its reaction form homogeneous cylinder, with the reacted capillary of washed with methanol, wash away remaining reaction reagent, obtain.
Embodiment 4
Take 180mg tetramethoxy-silicane, 20mg 3-sulfydryl propyl trimethoxy silicane, 35mg polyethylene glycol, 500mg 0.01M formic acid in centrifuge tube, hydrolysis completely.Then, add 21mg MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and 1mg azodiisobutyronitrile, mix, make pre-polymerization liquid.Pre-polymerization liquid is inserted through in pretreated capillary, sealed at both ends, in 25 ℃ of temperature ranges, make its reaction form homogeneous cylinder, with the reacted capillary of washed with methanol, wash away remaining reaction reagent, obtain.
Embodiment 5
Take 170mg tetramethoxy-silicane, 30mg 3-sulfydryl propyl trimethoxy silicane, 33mg PEO, 500mg 0.01M acetic acid in centrifuge tube, hydrolysis completely.Then, add 15mg acrylamide and 1mg azobisisobutryamide chloride, mix, make pre-polymerization liquid.Pre-polymerization liquid is inserted through in pretreated capillary, sealed at both ends, in 60 ℃ of temperature ranges, make its reaction form homogeneous cylinder, with acetonitrile, rinse reacted capillary, wash away remaining reaction reagent, obtain.
Embodiment 6
Take 160mg tetramethoxy-silicane, 40mg 3-sulfydryl propyl trimethoxy silicane, 27mg PEO, 500mg 0.01M acetic acid in centrifuge tube, hydrolysis completely.Then, add 25mg acrylamide and 1mg azobisisobutryamide chloride, mix, make pre-polymerization liquid.Pre-polymerization liquid is inserted through in pretreated capillary, sealed at both ends, in 80 ℃ of temperature ranges, make its reaction form homogeneous cylinder, with acetonitrile, rinse reacted capillary, wash away remaining reaction reagent, obtain.
Claims (4)
1. a preparation method for organic-inorganic hybrid integral post, is characterized in that: with silane coupling reagent, form surface with the integral post skeleton of mercapto groups; Utilize " click chemistry reaction " between sulfydryl-bis-keys simultaneously, when monolithic silica column forms, will be bonded directly to integral post surface containing end carbon-carbon double bond function monomer, step is as follows:
1) by silane coupler
with
and the pore-foaming agent of reacting dose is hydrolyzed in formic acid or acetic acid solution, obtain solution 1;
2) initator of the function monomer of end carbon-carbon double bonds and the required reacting dose of generation " click chemistry reaction " is joined in solution 1, mix and make pre-polymerization liquid;
3) the made pre-polymerization liquid of upper step is inserted through in pretreated capillary, sealed at both ends, in 20 ℃～80 ℃ temperature ranges, make its reaction form homogeneous cylinder, with organic solvent, rinse reacted capillary, wash away remaining reaction reagent, obtain.
2. the preparation method of organic-inorganic hybrid integral post as claimed in claim 1, is characterized in that: described pore-foaming agent is polyethylene glycol, PEO or polyacrylamide.
3. the preparation method of organic-inorganic hybrid integral post as claimed in claim 1, is characterized in that: described initator is azodiisobutyronitrile, azobisisobutryamide chloride.
4. the preparation method of organic-inorganic hybrid integral post as claimed in claim 1, 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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| 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 |
| 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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| 《Modification of VTMS hybrid monolith via thiol-ene click chemistry for 》;Keyi Wang, Yingzhuang Chen, Huihui Yang, Yi Li, Lihua Nie, Shouz;《Talanta》;20120112;52-59 * |
| Keyi Wang, Yingzhuang Chen, Huihui Yang, Yi Li, Lihua Nie, Shouz.《Modification of VTMS hybrid monolith via thiol-ene click chemistry for 》.《Talanta》.2012, * |
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