CN103601840A - Preparation and solid-phase extraction methods of polyacrylamide immobilized ionic-liquid capillary monolithic column - Google Patents
Preparation and solid-phase extraction methods of polyacrylamide immobilized ionic-liquid capillary monolithic column Download PDFInfo
- Publication number
- CN103601840A CN103601840A CN201310579294.3A CN201310579294A CN103601840A CN 103601840 A CN103601840 A CN 103601840A CN 201310579294 A CN201310579294 A CN 201310579294A CN 103601840 A CN103601840 A CN 103601840A
- Authority
- CN
- China
- Prior art keywords
- polyacrylamide
- monolithic column
- acrylamide
- ionic liquid
- methylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to preparation and solid-phase extraction methods of a polyacrylamide immobilized ionic-liquid capillary monolithic column. The polyacrylamide immobilized ionic-liquid capillary monolithic column is prepared from glycidol methacrylate, acrylamide, N,N-methylene-bis-acrylamide and 1-aminopropyl-3-methylimidazol chloride. The preparation method comprises the steps: reacting glycidol methacrylate and 1-aminopropyl-3-methylimidazol chloride in a solution containing formamide, so as to form a monomer with ionic-liquid functional groups, then, adding the monomer acrylamide and a crosslinker N,N'-methylene-bis-acrylamide, and then, adding an initiator azodiisobutyronitrile in the presence of a pore-forming agent polyethylene glycol, so as to form a polyacrylamide immobilized ionic-liquid solution; heating to polymerize in a capillary tube, thereby preparing the polyacrylamide immobilized ionic-liquid capillary monolithic column. The preparation method is simple, the cost is low, the reaction conditions are easily controlled, and the monolithic column has relatively good mechanical strength; when the monolithic column is applied to solid-phase extraction, the extraction capacity is large, the recovery rate is high, and the reproducibility is good, so that the monolithic column is applicable to carboxylic-acid compound extraction.
Description
Technical field
The present invention relates to stratographic analysis Sample Pretreatment Technique Used, particularly a kind of preparation of polyacrylamide matrix immobilization ionic liquid capillary monolithic column and for the method for Solid-Phase Extraction.
Background technology
Solid-Phase Extraction is as a kind of Sample Pretreatment Technique Used of extensively taking, utilize the feature of the capacity variance that analyte is adsorbed in different media, effectively that target compound is separated with interfering component, strengthened the analyte Detection capability of trace analysis thing particularly, also improved the rate of recovery of sample simultaneously.This technology is not only suitable for Trace Organic Compounds in extracting and enriching food and environmental water sample, and the enrichment of determined component in applicable biological sample.The better sorbent material of current development selectivity is the field of enlivening of Solid-Phase Extraction research.
In recent years, because integral material is by the method for in-situ polymerization, can be prepared in various upholders, such as being prepared in the injector syringe, Tip head, kapillary, chip channel etc. of stainless steel tube, polypropylene material, easily realize the regulation and control to integral post pore structure, surface properties, specific surface area.For the column extractor of loaded particles sorbent material, adopt integral material as sorbent material, not only saved loaded down with trivial details filling process, without filling sieve plate or sintering plunger, and in integral material, distinctive through hole is liquid mobilely provides large hole path, with convective mass transfer, replaced diffusion mass transfer slowly, resistance to mass transfer is obviously reduced, be conducive to the raising of extraction efficiency, thereby obtained increasing concern.
Ionic liquid refers to the organic molten salt being in a liquid state under room temperature (or a little higher than room temperature), by specific volume relatively large, the asymmetric organic cation of structure and the relatively little inorganic anion of volume form, have advantages of that volatility is low, thermostability and chemical stability is good, with water and the adjustable viscosity of organic solvent and solvability and to organism and the good extraction ability of metal ion, the novel green solvent that is considered to a kind of alternative conventional solvent, is widely used in sample pretreatment.Immobilization ionic liquid be by ionic liquid immobilization on organic polymer material or inorganic porous material, thereby obtain the solid matter that supported ion liquid or surface have ionic liquid structure, the immobilization ionic liquid making has the characteristic of ionic liquid and porous carrier materials concurrently.Compare with free state ionic liquid, immobilization ionic liquid can increase specific surface area, thereby improves its utilising efficiency and stability, and the consumption of ionic liquid obviously reduces, and the separation after use, recycling easily realize.In Solid-Phase Extraction, immobilization ionic liquid is mainly as coating (Y. Meng, V. Pino, the J. L. Anderson of solid-phase microextraction, Anal. Chim. Acta 2011,687,141-149), or immobilized at polymer beads (W. Bi, M. Tian, K. H. Row, J. Sep. Sci. 2010,33,1739-1745) and silica gel particle on (G. Fang, J. Chen, J. Wang, J. He, S. Wang, J. Chromatogr. A 2010,1217,1567-1574).
CN102500346A proposes a kind of employing sol-gel and the surface-functionalized technology of golden nanometer particle is prepared novel ion liquid silica gel capillary monolithic column stationary phase, for capillary liquid chromatography and capillary electrochromatography separation of benzene amine or polynuclear aromatics compounds.But it connects silica gel and ionic liquid imidazoles bromine salt with golden nanometer particle, there is cost height and make the problems such as difficulty, be difficult to apply in the trace organic substance abstraction technique of food and environmental water sample.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of polymkeric substance being comprised of polyacrylamide immobilization ionic liquid, adopts this polymkeric substance to prepare capillary monolithic column, for the Solid-Phase Extraction to carboxylic acid compound.
The present invention realizes above-mentioned purpose by the following technical solutions:
Polyacrylamide immobilization ion liquid polymer is by glycidyl methacrylate, acrylamide, N, and N-methylene-bis acrylamide and 1-aminopropyl-3-Methylimidazole villaumite form.
The elementary cell of polyacrylamide immobilization ionic liquid chemical structural formula is:
The synthetic method of polyacrylamide immobilization ion liquid polymer, comprises the following steps:
Glycidyl methacrylate is reacted in containing formamide soln with 1-aminopropyl-3-Methylimidazole villaumite, form the monomer with ion liquid functional group; Add subsequently monomer acrylamide, linking agent N, N '-methylene-bisacrylamide, under the existence of pore-creating agent polyoxyethylene glycol, then adds initiator Diisopropyl azodicarboxylate to form polyacrylamide immobilization ionic liquid solution.
The mass ratio of described glycidyl methacrylate and 1-aminopropyl-3-Methylimidazole villaumite is 1:1～1:3.
Described acrylamide and N, N '-methylene-bisacrylamide is 1:1:1～1:3:3 with the mass ratio of the monomer of rolling into a ball with ion liquid functional.
The preparation method of polyacrylamide immobilization ionic liquid capillary monolithic column, comprises the following steps:
A, first by quartz capillary successively through persalt, water, sodium hydroxide, water, washed with methanol, and after dry, add with after the methanol solution of γ-2 methyl allyl acyloxypropyl trimethoxysilane and the silicon hydroxyl reaction on capillary wall, dry up stand-by;
B, the polyacrylamide immobilization gas ions solution of having prepared is injected into above-mentioned in the kapillary of vinyl modified, in 65～80 ℃ of waters bath with thermostatic control, polyreaction is 20～24 hours, use again polymkeric substance in washed with methanol kapillary, obtain polyacrylamide immobilization ion capillary monolithic column.
Polyacrylamide immobilization ionic liquid capillary monolithic column is used for the method for Solid-Phase Extraction carboxylic acid compound:
Polyacrylamide immobilization ionic liquid capillary monolithic column is first used to distilled water flushing, then use the hydrochloride buffer balance capillary monolithic column of pH 6.3; After flow velocity loading 60～80 min by carboxylic acid compound with 10～13.3 μ L/min, the formic acid of employing 10% and 40% acetonitrile mixing solutions are with flow velocity wash-out 4～10 min of 4～10 μ L/min, to collect elutriant with after 5000～6000 rpm whizzer high speed centrifugations, with Ultra Performance Liquid Chromatography instrument, carry out stratographic analysis.
Advantage of the present invention and positively effect are: first polyacrylamide immobilization ionic liquid solution is prepared in kapillary, the method of preparing polyacrylamide immobilization ionic liquid capillary monolithic column is simple, with low cost, easy control of reaction conditions, the novel capillary integral post making has stronger physical strength, is applied to Solid-Phase Extraction, and the rate of recovery is high, loading capacity is large, favorable reproducibility, is applicable to extract carboxylic acid compound.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of polyacrylamide immobilization ionic liquid preparation method A;
Fig. 2 a and Fig. 2 b are the schematic diagram of polyacrylamide immobilization ionic liquid preparation method B;
Fig. 3 is that the polyacrylamide immobilization ionic liquid capillary monolithic column of embodiment 1 preparation is for the color atlas of Solid-Phase Extraction soda pop carboxylic acid compound.(A) direct injection; (B) extraction sample introduction.In Fig. 3, peak 1 is m-Salicylic acid; Peak 2 is phenylformic acid; Peak 3 is styracin; Peak 4 is 2,4 dichlorophenoxyacetic acid; Peak 5 is m-TrifluoromethylcinnaAcid Acid;
Fig. 4 is that the polyacrylamide immobilization ionic liquid capillary monolithic column of embodiment 2 preparations is for the color atlas of Solid-Phase Extraction mineral water carboxylic acid compound.(A) direct injection; (B) extraction sample introduction.In Fig. 4, peak 1 is PCA; Peak 2 is P-hydroxybenzoic acid; Peak 3 is m-Salicylic acid; Peak 4 is forulic acid; Peak 5 is 2-hydroxyl-3-naphthoic acid.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1: as shown in Figure 1, the active amino that the epoxy group(ing) that glycidyl methacrylate is contained and 1-aminopropyl-3-Methylimidazole villaumite contain reacts in methane amide, formation is with the monomer of ion liquid functional group, add subsequently monomer acrylamide, linking agent N, N '-methylene-bisacrylamide, at pore-creating agent, (PEG 8000, PEG 10000) existence under, add initiator Diisopropyl azodicarboxylate (AIBN), above-mentioned polymers soln is injected in the quartz capillary of vinyl modified, in 80 ℃ of thermostat water baths, react 20 hours, finally use washed with methanol stand-by.
Vinyl modified pre-treatment capillaceous: quartz capillary is used after 0.5 mol/L HCl, distilled water, 0.5 mol/L NaOH, distilled water, washed with methanol 30 min successively, with nitrogen, dry up, again with syringe by 50%(v/v) the methanol solution of γ-2 methyl allyl acyloxypropyl trimethoxysilane pour in kapillary, with silica gel by after sealed at both ends, at room temperature react 12 hours, with methyl alcohol, γ-2 methyl allyl acyloxypropyl trimethoxysilane residual in kapillary is rinsed well again, and capillary column is placed in gas-chromatography stove, at the N of 70 ° of C
2flow down dry 1 hour.
By function monomer glycidyl methacrylate 20.6 mg, ionic liquid 1-aminopropyl-3-Methylimidazole villaumite 30.8 mg, solvent pore-creating agent methane amide 679.4 mg that hold concurrently, with NaOH, be adjusted to pH 8-9, at room temperature mix, 40 ° of C react 1 hour, formation is with the monomer of ion liquid functional group, subsequently, at but 10 min of 2-8 ° of C refrigerator and cooled, add monomer acrylamide 10.0 mg, linking agent N, N '-methylene-bisacrylamide 20.0 mg, pore-creating agent PEG 8,000 45 mg and PEG 10,000 25 mg, initiator Diisopropyl azodicarboxylate 0.5 mg, ultrasonic mixing at room temperature, pour in the quartz capillary of vinyl modified, with silica gel, seal, in the thermostat water bath of 80 ° of C, react 20 hours, after polyreaction completes, with washed with methanol quartz capillary, remove unreacted monomer, linking agent and pore-creating agent, obtain polyacrylamide immobilization ionic liquid capillary monolithic column.
Embodiment 2: as shown in Figure 2 a and 2 b, by monomer glycidyl methacrylate and acrylamide, linking agent N, N '-methylene-bisacrylamide, at pore-creating agent, (PEG 8000, PEG 10000, methane amide) under existence, add initiator Diisopropyl azodicarboxylate, above-mentioned polymers soln is injected in the quartz capillary of vinyl modified, in the thermostat water bath of 65 ° of C, react and within 24 hours, generate acrylamide-N, N '-methylene-bisacrylamide-glycidyl methacrylate polymkeric substance, use subsequently the unreacted function monomer of washed with methanol and linking agent, use again buffered soln balance integral post, finally, the ionic liquid 1-aminopropyl-3-Methylimidazole villaumite dissolving with buffered soln slowly rinses above synthetic integral post, ionic liquid 1-aminopropyl-3-Methylimidazole villaumite is immobilized on integral material.
Described acrylamide, N, the mass ratio between N '-methylene-bisacrylamide and glycidyl methacrylate is 1:1:1～1:3:3; Described acrylamide-N, the mass ratio of N '-methylene-bisacrylamide-glycidyl methacrylate polymkeric substance and 1-aminopropyl 3-Methylimidazole villaumite is 1:1～1:3.
Vinyl modified pre-treatment capillaceous is with embodiment 1.
By function monomer glycidyl methacrylate 20.6 mg and acrylamide 10.0 mg, linking agent N, N '-methylene-bisacrylamide 20.0 mg, solvent pore-creating agent methane amide 679.4 mg that hold concurrently, pore-creating agent PEG 8,000 45 mg and PEG 10,000 25 mg, initiator Diisopropyl azodicarboxylate 0.5 mg, ultrasonic mixing at room temperature, pour in the quartz capillary of vinyl modified, with silica gel, seal, in the thermostat water bath of 65 ° of C, react 24 hours, after polyreaction completes, with washed with methanol quartz capillary, remove unreacted monomer, linking agent and pore-creating agent.Use again 10 mM Tris-HCl(pH 8.0) solution flushing pillar 30 min, subsequently, ionic liquid 1-aminopropyl-3-Methylimidazole villaumite of 30.8 mg/mL (is dissolved in to 10 mM Tris-HCl, pH 8.0) with flow velocity slowly, rinse the as above integral post of preparation, obtain polyacrylamide immobilization ionic liquid capillary monolithic column, stand-by.
Embodiment 3: for verifying the Solid-Phase Extraction performance of the prepared polyacrylamide immobilization ionic liquid capillary monolithic column of example 1 to carboxylic acid compound, the prepared polyacrylamide immobilization ionic liquid capillary monolithic column of take is spe medium, adopts Ultra Performance Liquid Chromatography to analyze soda pop.
Soda pop sample preparation: measure soda pop 1 mL, with the hydrochloric acid buffer solution dilution of pH 6.3, cause 10 mL, after nylon leaching film by 0.45 μ m, the styracin, the extraction of m-TrifluoromethylcinnaAcid Acid standardized solution sample introduction that add m-Salicylic acid, phenylformic acid, 2,4 dichlorophenoxyacetic acid and the 0.04 μ g/mL of 0.02 μ g/mL.
Extraction conditions: adopt the made capillary monolithic column of example 1, first water rinses, hydrochloric acid buffer solution balance capillary monolithic column with pH 6.3, flow velocity loading 80 min with 10 μ L/min, finally adopt 10% formic acid and 40% acetonitrile mixing solutions, with flow velocity wash-out 4 min of 10 μ L/min, collect elutriant, with after 6000 rpm high speed centrifugations, with Ultra Performance Liquid Chromatography, analyze.
Chromatographiccondition: analytical column is Acclaim
tMrSLC 120 C18 (2.1 * 150 mm, 2.2 μ m), the 10 mM ammonium formiates that moving phase is 58% and 0.1% formic acid mixing buffered soln and 42% acetonitrile, flow velocity 0.3 mL/min, sample introduction 10 μ L, 30 ° of C of column temperature, detect wavelength 230 nm.
Fig. 3 color atlas (A) is extraction sample introduction, and color atlas (B) is direct injection.As shown in Fig. 3 (B), before soda pop sample does not pass through Solid-Phase Extraction, the sample signal of detection is lower.As shown in Fig. 3 (A), soda pop sample is through after fiber material provided by the invention carries out Solid-Phase Extraction, and each compound obtains good enrichment with separated, and is not subject to impurity and disturbs, and elution peak 1 is m-Salicylic acid successively; 2 is phenylformic acid; 3 is styracin; 4 is 2,4 dichlorophenoxyacetic acid; 5 is m-TrifluoromethylcinnaAcid Acid, and the rate of recovery is respectively 85.7%, 95.1%, 97.4%, 96.8% and 106.1%, and the relative standard deviation of extractive analysis is less than 8%, illustrates that this Solid-Phase Extraction material is applicable to the analysis of soda pop.
Embodiment 4: for verifying the Solid-Phase Extraction performance of the prepared polyacrylamide immobilization ionic liquid capillary monolithic column of example 2 to carboxylic acid compound, the prepared polyacrylamide immobilization ionic liquid capillary monolithic column of take is spe medium, adopts Ultra Performance Liquid Chromatography to analyze mineral water.
Mineral water sample preparation: measure mineral water 1 mL, with the hydrochloric acid buffer solution dilution of pH 6.3, cause 10 mL, after nylon leaching film by 0.45 μ m, add the m-Salicylic acid of 0.02 μ g/mL and the PCA of 0.01 μ g/mL, P-hydroxybenzoic acid, forulic acid and the extraction of 2-hydroxyl-3-naphthoic acid standardized solution sample introduction.
Extraction conditions: adopt the made capillary monolithic column of example 2, first water rinses, hydrochloric acid buffer solution balance capillary monolithic column with pH 6.3, flow velocity loading 60 min with 13.3 μ L/min, finally adopt 10% formic acid and 40% acetonitrile mixing solutions, with flow velocity wash-out 10 min of 4 μ L/min, collect elutriant, with after 5000 rpm high speed centrifugations, with Ultra Performance Liquid Chromatography, analyze.
Chromatographiccondition: analytical column is Acclaim
tMrSLC 120 C18 (2.1 * 150 mm, 2.2 μ m), the 0.1% first aqueous acid that mobile phase A is; Mobile phase B is pure acetonitrile, gradient: 0-4 min 35%B, 4-4.1 min 35%B-80%B, 4.1-12 min 80%B; Flow velocity 0.3 mL/min, sample introduction 10 μ L, 30 ° of C of column temperature, detect wavelength 254 nm.
Fig. 4 color atlas (A) is extraction sample introduction, and color atlas (B) is direct injection.As shown in Fig. 4 (B), mineral water sample does not detect sample signal before passing through Solid-Phase Extraction, lower than the detectability of Ultra Performance Liquid Chromatography.As shown in Figure 4 (A), mineral water sample is through after fiber material provided by the invention carries out Solid-Phase Extraction, and each compound obtains good enrichment with separated, and is not subject to impurity and disturbs, and elution peak 1 is PCA successively; 2 is P-hydroxybenzoic acid; 3 is m-Salicylic acid; 4 is forulic acid; 5 is 2-hydroxyl-3-naphthoic acid, and the rate of recovery is respectively 81.3%, 92.6%, 97.3%, 90.7% and 84.2%, and the relative standard deviation of extractive analysis is less than 10%, illustrates that this Solid-Phase Extraction material is applicable to the analysis of mineral water.
Claims (9)
1. polyacrylamide immobilization ion liquid polymer, is characterized in that: by glycidyl methacrylate, acrylamide, N, N-methylene-bis acrylamide and 1-aminopropyl-3-Methylimidazole villaumite form.
2. polyacrylamide immobilization ion liquid polymer according to claim 1, is characterized in that: the elementary cell of polyacrylamide immobilization ionic liquid chemical structural formula is:
。
3. the synthetic method of polyacrylamide immobilization ion liquid polymer, is characterized in that comprising the following steps:
Glycidyl methacrylate is reacted in containing formamide soln with 1-aminopropyl-3-Methylimidazole villaumite, form the monomer with ion liquid functional group; Add subsequently monomer acrylamide, linking agent N, N '-methylene-bisacrylamide, under the existence of pore-creating agent polyoxyethylene glycol, then adds initiator Diisopropyl azodicarboxylate to form polyacrylamide immobilization ionic liquid solution.
4. the synthetic method of polyacrylamide immobilization ion liquid polymer according to claim 3, it is characterized in that described glycidyl methacrylate and the mass ratio of 1-aminopropyl-3-Methylimidazole villaumite are 1:1～1:3, described acrylamide and N, N '-methylene-bisacrylamide is 1:1:1～1:3:3 with the mass ratio of the monomer of rolling into a ball with ion liquid functional.
5. the preparation method of polyacrylamide immobilization ionic liquid capillary monolithic column, is characterized in that comprising the following steps:
A, first by quartz capillary successively through persalt, water, sodium hydroxide, water, washed with methanol, and after dry, add with after the methanol solution of γ-2 methyl allyl acyloxypropyl trimethoxysilane and the silicon hydroxyl reaction on capillary wall, dry up stand-by;
B, the polyacrylamide immobilization gas ions solution of having prepared is injected into above-mentioned in the kapillary of vinyl modified, in 65～80 ℃ of waters bath with thermostatic control, polyreaction is 20～24 hours, use again polymkeric substance in washed with methanol kapillary, obtain polyacrylamide immobilization ion capillary monolithic column.
6. according to the preparation method of polyacrylamide immobilization ionic liquid capillary monolithic column described in claim 3 or 5, it is characterized in that the active amino that epoxy group(ing) that glycidyl methacrylate is contained and 1-aminopropyl-3-Methylimidazole villaumite contain reacts in methane amide, formation is with the monomer of ion liquid functional group, add subsequently monomer acrylamide, linking agent N, N '-methylene-bisacrylamide, at pore-creating agent (PEG8000, PEG10000) under existence, add initiator Diisopropyl azodicarboxylate, above-mentioned polymers soln is injected in the quartz capillary of vinyl modified, in 80 ℃ of waters bath with thermostatic control, react 20 hours, finally use washed with methanol stand-by.
7. according to the preparation method of polyacrylamide immobilization ionic liquid capillary monolithic column described in claim 5, it is characterized in that monomer glycidyl methacrylate and acrylamide, linking agent N, N '-methylene-bisacrylamide, at pore-creating agent (PEG8000, PEG10000, methane amide) under existence, add initiator Diisopropyl azodicarboxylate, above-mentioned polymers soln is injected in the quartz capillary of vinyl modified, in the water bath with thermostatic control of 65 ° of C, react and within 24 hours, generate acrylamide-N, N '-methylene-bisacrylamide-glycidyl methacrylate polymkeric substance, use subsequently the unreacted function monomer of washed with methanol and linking agent, use again buffered soln balance integral post, finally, the ionic liquid 1-aminopropyl-3-Methylimidazole villaumite dissolving with buffered soln slowly rinses above synthetic integral post, described ionic liquid 1-aminopropyl-3-Methylimidazole villaumite is immobilized on integral material.
8. according to the preparation method of polyacrylamide immobilization ionic liquid capillary monolithic column described in claim 7, it is characterized in that described acrylamide, N, the mass ratio between N '-methylene-bisacrylamide and glycidyl methacrylate is 1:1:1～1:3:3; Described acrylamide-N, the mass ratio of N '-methylene-bisacrylamide-glycidyl methacrylate polymkeric substance and 1-aminopropyl 3-Methylimidazole villaumite is 1:1～1:3.
9. polyacrylamide immobilization ionic liquid capillary monolithic column, for the method for Solid-Phase Extraction carboxylic acid compound, is characterized in that comprising the following steps:
Polyacrylamide immobilization ionic liquid capillary monolithic column is first used to distilled water flushing, then use the hydrochloride buffer balance capillary monolithic column of pH 6.3; After flow velocity loading 60～80 min by carboxylic acid compound with 10 ~ 13.3 μ L/min, the formic acid of employing 10% and 40% acetonitrile mixing solutions are with flow velocity wash-out 4～10 min of 4～10 μ L/min, to collect elutriant with after 5000～6000 rpm whizzer high speed centrifugations, with Ultra Performance Liquid Chromatography instrument, carry out stratographic analysis.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310579294.3A CN103601840B (en) | 2013-11-19 | 2013-11-19 | The preparation of polyacrylamide immobilization ionic liquid capillary monolithic column and solid phase extraction method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310579294.3A CN103601840B (en) | 2013-11-19 | 2013-11-19 | The preparation of polyacrylamide immobilization ionic liquid capillary monolithic column and solid phase extraction method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103601840A true CN103601840A (en) | 2014-02-26 |
| CN103601840B CN103601840B (en) | 2015-07-29 |
Family
ID=50120112
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310579294.3A Expired - Fee Related CN103601840B (en) | 2013-11-19 | 2013-11-19 | The preparation of polyacrylamide immobilization ionic liquid capillary monolithic column and solid phase extraction method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103601840B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104549181A (en) * | 2015-02-06 | 2015-04-29 | 武汉大学 | Preparation method and application of hydrophilic methacrylamide polymer monolithic column |
| CN105148559A (en) * | 2015-09-09 | 2015-12-16 | 宁波工程学院 | Preparation of embedded attapulgite capillary monolithic column and method for using capillary monolithic column for solid phase micro extraction |
| CN105311858A (en) * | 2014-07-28 | 2016-02-10 | 中国科学院大连化学物理研究所 | Pentafluorobenzyl imidazolium salt ionic liquid hybrid monolithic column, and preparation method and application thereof |
| CN105771318A (en) * | 2016-05-05 | 2016-07-20 | 福州大学 | Ionic liquid functionalized organic polymerized monolithic column and preparation method thereof |
| CN107684905A (en) * | 2017-09-20 | 2018-02-13 | 宁波工程学院 | The preparation method of organic inorganic hybridization integral post based on attapulgite and its application in separation |
| CN115290806A (en) * | 2022-08-01 | 2022-11-04 | 宁波工程学院 | Method for solid-phase extraction of biogenic amine through hydrophilicity and cation exchange |
| CN115332631A (en) * | 2022-10-12 | 2022-11-11 | 常州目天智储科技有限公司 | High-voltage electrolyte and high-voltage lithium ion battery |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060138052A1 (en) * | 2004-12-28 | 2006-06-29 | Polymerics Gmbh | Sorbent and process of solid phase extraction |
| CN101185833A (en) * | 2007-09-11 | 2008-05-28 | 浙江大学 | Regeneratable load type desulfurizing agent and preparation method thereof |
| US20090170973A1 (en) * | 2005-05-13 | 2009-07-02 | Bo Mattiasson | Macroporous hydrogels, their preparation and their use |
| CN102500346A (en) * | 2011-11-03 | 2012-06-20 | 广西师范大学 | Preparation method for ionic liquid silica gel capillary monolithic column stationary phase |
-
2013
- 2013-11-19 CN CN201310579294.3A patent/CN103601840B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060138052A1 (en) * | 2004-12-28 | 2006-06-29 | Polymerics Gmbh | Sorbent and process of solid phase extraction |
| US20090170973A1 (en) * | 2005-05-13 | 2009-07-02 | Bo Mattiasson | Macroporous hydrogels, their preparation and their use |
| CN101185833A (en) * | 2007-09-11 | 2008-05-28 | 浙江大学 | Regeneratable load type desulfurizing agent and preparation method thereof |
| CN102500346A (en) * | 2011-11-03 | 2012-06-20 | 广西师范大学 | Preparation method for ionic liquid silica gel capillary monolithic column stationary phase |
Non-Patent Citations (5)
| Title |
|---|
| GUOZHEN FANG ET AL: ""N-Methylimidazolium ionic liquid-functionalized silica as a sorbent for selective solid-phase extraction of 12 sulfonylurea herbicides in environmental water and soil samples"", 《JOURNAL OF CHROMATOGRAPHY A》, vol. 1217, 14 January 2010 (2010-01-14), pages 1567 - 1574 * |
| MIRA DAOUD-ATTIEH ET AL: ""Immunoglobulin G purification from bovine serum with pseudo-specific supermacroporous cryogels"", 《SEPARATION AND PURIFICATION TECHNOLOGY》, vol. 118, 27 August 2013 (2013-08-27), pages 816 - 822, XP028739067, DOI: 10.1016/j.seppur.2013.08.026 * |
| WENTAO BI ET AL: ""Solid-phase extraction of matrine and oxymatrine from Sophora Flavescens Ait using amino-imidazolium polymer"", 《JOURNAL OF SEPARATION SCIENCE》, vol. 33, no. 12, 30 April 2010 (2010-04-30), pages 1739 - 1745 * |
| YUNJING MENG ET AL: ""Role of counteranions in polymeric ionic liquid-based solid-phase microextraction coatings for the selective extraction of polar compounds"", 《ANALYTICA CHIMICA ACTA》, vol. 687, 27 November 2010 (2010-11-27), pages 141 - 149, XP028132506, DOI: 10.1016/j.aca.2010.11.046 * |
| 彭永兴: ""咪唑类离子液体色谱填料的合成与表征"", 《中国优秀硕士学位论文全文数据库·工程科技I辑》, 15 January 2011 (2011-01-15) * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105311858A (en) * | 2014-07-28 | 2016-02-10 | 中国科学院大连化学物理研究所 | Pentafluorobenzyl imidazolium salt ionic liquid hybrid monolithic column, and preparation method and application thereof |
| CN105311858B (en) * | 2014-07-28 | 2017-03-15 | 中国科学院大连化学物理研究所 | A kind of PFBBR imidazolium ionic liquid hydridization integral post and its preparation and application |
| CN104549181A (en) * | 2015-02-06 | 2015-04-29 | 武汉大学 | Preparation method and application of hydrophilic methacrylamide polymer monolithic column |
| CN104549181B (en) * | 2015-02-06 | 2017-01-11 | 武汉大学 | Preparation method and application of hydrophilic methacrylamide polymer monolithic column |
| CN105148559A (en) * | 2015-09-09 | 2015-12-16 | 宁波工程学院 | Preparation of embedded attapulgite capillary monolithic column and method for using capillary monolithic column for solid phase micro extraction |
| CN105771318A (en) * | 2016-05-05 | 2016-07-20 | 福州大学 | Ionic liquid functionalized organic polymerized monolithic column and preparation method thereof |
| CN107684905A (en) * | 2017-09-20 | 2018-02-13 | 宁波工程学院 | The preparation method of organic inorganic hybridization integral post based on attapulgite and its application in separation |
| CN115290806A (en) * | 2022-08-01 | 2022-11-04 | 宁波工程学院 | Method for solid-phase extraction of biogenic amine through hydrophilicity and cation exchange |
| CN115290806B (en) * | 2022-08-01 | 2024-05-28 | 宁波工程学院 | Method for solid phase extraction of biogenic amine by hydrophilic effect and cation exchange |
| CN115332631A (en) * | 2022-10-12 | 2022-11-11 | 常州目天智储科技有限公司 | High-voltage electrolyte and high-voltage lithium ion battery |
| CN115332631B (en) * | 2022-10-12 | 2023-03-24 | 常州目天智储科技有限公司 | High-voltage electrolyte and high-voltage lithium ion battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103601840B (en) | 2015-07-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103601840B (en) | The preparation of polyacrylamide immobilization ionic liquid capillary monolithic column and solid phase extraction method | |
| Hu et al. | Preparation and evaluation of a porous monolithic capillary column for microextraction of estrogens from urine and milk samples online coupled to high-performance liquid chromatography | |
| CN106959349B (en) | A kind of microtrabeculae enrichment sample injection method | |
| Huang et al. | Preparation of a new polymeric ionic liquid-based monolith for stir cake sorptive extraction and its application in the extraction of inorganic anions | |
| CN106179237B (en) | A kind of nanofiber and preparation method thereof of extracting and enriching heavy metal ion | |
| CN103497277B (en) | Scutellarin molecularly imprinted polymer and its preparation method and application | |
| CN103558320B (en) | Boric acid is affine integral post solid-phase microextraction-high performance liquid chromatography on-line coupled system | |
| CN104941611A (en) | Preparation method of novel grafting high-capacity dendrimer ion chromatography stationary phase stuffing | |
| CN105056913B (en) | A kind of preparation method of the In-tube SPME compound post for phosphoric acid extraction peptide | |
| CN102935390A (en) | Preparation method of carbon nano tube latex agglomeration type anion chromatographic packing | |
| CN103833885B (en) | A kind of ion liquid polymer kapillary micro-extraction integral post and preparation method thereof | |
| CN101334386B (en) | Determination method for plant medicine blood plasma amygdalin for strengthening the body resistance | |
| Collins et al. | A review of recent advances in electrochemically modulated extraction methods | |
| CN101612555A (en) | A kind of stirring rod for whole molecularly imprinted polymer and preparation method thereof | |
| CN102169109B (en) | Method for preparing estrogen substitution template molecular imprinting solid phase micro extraction head | |
| CN104316628B (en) | Molecule crowding agent and ionic liquid are the method that pore-foaming agent prepares trace integral post | |
| CN103512849B (en) | The device detected for dispersive liquid-liquid microextraction spectrum on line and detection method | |
| Zhang et al. | Preparation and characterization of polymer solid-phase microextraction monolith modified with gold nanoparticles | |
| CN105080515B (en) | MIP SPME extracting fibers and extraction platform and application | |
| Yang et al. | Molecularly imprinted on-line solid-phase extraction combined with chemiluminescence for the determination of pazufloxacin mesilate | |
| CN104610498B (en) | A kind of preparation method based on boron affinity interaction porous entirety spe medium | |
| CN103884802B (en) | A kind of memory loss shellfish poison molecular engram integral column and application thereof | |
| CN106492506A (en) | Polymer-modified integral post of a kind of nanometer gold and its preparation method and application | |
| CN108178810A (en) | The preparation and its application of a kind of reverse phase/anion exchange mixed mode polymer | |
| CN103990298B (en) | A kind of preparation method of surface and hydrophilic outer macropore organic-inorganic hybridization monolithic column |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150729 Termination date: 20161119 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |