CN102993229B - Amphoteric electrolyte-modified hybrid silica gel material and solid-phase extraction method thereof - Google Patents
Amphoteric electrolyte-modified hybrid silica gel material and solid-phase extraction method thereof Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J43/00—Amphoteric ion-exchange, i.e. using ion-exchangers having cationic and anionic groups; Use of material as amphoteric ion-exchangers; Treatment of material for improving their amphoteric ion-exchange properties
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- B01J47/00—Ion-exchange processes in general; Apparatus therefor
- B01J47/014—Ion-exchange processes in general; Apparatus therefor in which the adsorbent properties of the ion-exchanger are involved, e.g. recovery of proteins or other high-molecular compounds
Abstract
The invention discloses an amphoteric electrolyte-modified hybrid silica gel material. An amphoteric electrolyte containing an amino group and a carboxyl group is bonded on a branch of the hybrid silica gel to obtain a hybrid silica gel material with an amphoteric group on the surface. A preparation method of the hybrid silica gel material comprises the following steps of: forming a hybrid silica gel material containing amino on the surface by taking tetraethoxy silane and aminopropyltriethoxy silane as precursor molecules and taking hexadecyl trimethyl ammonium bromide as a template agent; enabling the hybrid silica gel to react with the aldehyde group of glutaraldehyde to generate a hybrid silica gel material with a C=N bond; enabling the aldehyde group at the other end of glutaraldehyde on the hybrid silica gel material to react with the amphoteric electrolyte with the amino group and the carboxyl group to generate a hybrid silica gel material with double C=N bonds; and reducing with NaCNBH3 to reduce C=N into C-N to form a hybrid silica gel material with multiple -NH2 groups and multiple -COOH groups. A solid-phase extraction column or solid-phase extraction capillary tube prepared from the hybrid silica gel material gives play to the advantages of anion-cation exchange on the same material at the same time by controlling the pH value, and realizes synchronous extraction of acid, neutral and alkali samples; and moreover, the adsorption and desorption are fast, the reproducibility and recovery rate are high, and the speed and precision of detection and separation can be improved.
Description
Technical field
The present invention relates to Sample Pretreatment Technique Used field, the hybridization silica gel material of particularly a kind of amphotericeledrolyte modification and solid phase extraction method thereof.
Background technology
Solid phase extraction techniques (SPE) is employing selective adsorption, the mode of selective elution carries out enrichment, separation, purifying to sample, comprise the physical extraction process of liquid phase and solid phase, not only be 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 composite adsorption mechanism main representative of Solid-Phase Extraction material is Oasis MCX and Oasis WCX, its adsorption mechanism is in conjunction with anti-phase reservation and strong (weak) cationic exchange, be confined to analyze basic sample solution, or Oasis MAX and Oasis WAX, its adsorption mechanism, in conjunction with anti-phase reservation and strong (weak) anionresin, is confined to analyze acidic sample.If acidity, neutrality and basic sample solution need be analyzed simultaneously, need by Oasis MCX(WCX) and Oasis MAX(WAX) series connection uses (M. Lav é n, T. Alsberg, Y. Yu, M. Adolfsson-Erici, H. Sun, J. Chromatogr. A 2009,1216,49 – 62).But same solid-phase extraction column is analyzed while failing to realize acid, neutral and basic sample solution.The SPE post of Varian such as Huang extracts acidity, neutrality and weakly alkaline sample simultaneously, the rate of recovery is (RSD<9%) between 70%-120%, its extraction mechanisms is also composite adsorption mechanism, comprises anti-phase and anionresin, reverse phase mechanism plays a major role (Z. P. Huang, X. H. Chen, J. Wijsbeek, J. P. Franke, R. A. J. Anal. Toxicol. 1996,20,248-254).
A kind of hybrid inorganic-organic silica gel material adopting sol-gel method to prepare of latest developments, there is inorganic and organic constituent in this material, inorganic part provides the polymeric skeleton of mechanically stable simultaneously; Organic group, then for improving material property, avoids the defect that stability of material prepared by traditional deriving method is poor.C8 and sulfonic group are modified on hybridization silica gel material by Zheng etc., gather anti-phase and mechanism that is strong cation exchange, Solid-Phase Extraction has been carried out to the sulfa drugs in milk, stable (M. M. Zheng between pH 1.0-10.5, G. D. Ruan, Y. Q.Feng, J. Chromatogr. A 2009,1216,7739-7746.).
At present, cation exchange mechanism and anion exchanged mechanism just in conjunction with anti-phase and cloudy (sun) ion-exchange, are not combined on same stationary phase by Solid-Phase Extraction composite adsorption mechanism, realize extraction that is acid, neutral and basic sample solution.
Amphotericeledrolyte (Ampholine) is the mixture of a polyamine species base and multi-carboxy compound, has very strong surge capability, and under different pH conditions, the charged situation of ion surface is different.Under the condition of acidity, amido mainly becomes positively charged lotus; And under the condition of alkalescence, carboxyl mainly brings negative charge.Therefore, by regulating pH, changing the electrically charged state of ion surface, well realizing the conversion of anion exchanged mechanism and cation exchange mechanism, the extraction of acidity, neutrality and basic sample solution can be realized respectively.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of hybridization silica gel material being modified hybridisation silica gel surface by amphotericeledrolyte (Ampholine), thus cation exchange mechanism and anion exchanged mechanism are combined on same stationary phase, the extraction of acidity, neutrality and basic sample solution can be realized respectively.
The technical solution used in the present invention is: the hybridization silica gel material that amphotericeledrolyte is modified, and on hybridisation silica gel side chain, bonding contains the amphotericeledrolyte of amido and carboxyl, obtains the hybridization silica gel material of surface band amphiprotic group, and chemical structural formula elementary cell is:
The preparation method of the hybridization silica gel material that amphotericeledrolyte is modified, comprises the following steps:
A), with tetraethoxysilane and aminopropyl triethoxysilane for precursor molecule, being template with cetyl trimethylammonium bromide, take dehydrated alcohol as solvent, forms the hybridization silica gel material of surface containing amido;
B), under pH8.0 condition, the aldehyde radical of above-mentioned hybridisation silica gel and excessive glutaraldehyde is reacted the hybridization silica gel material of green tape C=N key;
C), equally under pH8.0 condition, the glutaraldehyde the other end aldehyde radical on above-mentioned hybridization silica gel material and the both sexes electrolytic reaction of band amido and carboxyl are generated the hybridization silica gel material being with two C=N keys;
D) by the hybridization silica gel material NaCNBH of two C=N keys of c) step generation
3reduction, the hybridization silica gel material making C=N be reduced into C-N is formed the many-NH of band
2with the hybridization silica gel material of many-COOH.
With the hybridization silica gel material of polyamines base and many carboxyls, have very strong surge capability, under different pH conditions, the charged situation of ion surface is different.Under the condition of acidity, amido mainly becomes positively charged lotus; And under the condition of alkalescence, carboxyl mainly brings negative charge.Therefore, by regulating pH, changing the electrically charged state of ion surface, the extraction of acidity, neutrality and basic sample solution can be realized respectively.
The solid-phase extraction column utilizing the hybridization silica gel material of band polyamines base and many carboxyls to make or solid phase extraction capillary, by regulable control pH value, change the electrically charged state of ion surface, a kind of material plays the advantage of cation and anion exchange simultaneously, better realization is to extraction while acid, neutral and basic sample solution, and sorption and desorption speed is fast, favorable reproducibility, the rate of recovery is high, can improve and detect and the speed be separated and precision.
Accompanying drawing explanation
Fig. 1 be hybridization silica gel material of the present invention prepare schematic diagram;
Fig. 2 is the scanning electron microscope (SEM) photograph of hybridization silica gel material of the present invention;
Fig. 3 is the Infrared spectroscopy figure of hybridization silica gel material of the present invention;
Fig. 4 is the neutrality of hybridization silica gel material of the present invention and the variation diagram of the basic sample solution rate of recovery and loading pH;
Fig. 5 is the neutrality of hybridization silica gel material of the present invention and the variation diagram of the basic sample solution rate of recovery and wash-out pH;
Fig. 6 is the neutrality of hybridization silica gel material of the present invention and the variation diagram of the basic sample solution rate of recovery and methanol concentration;
Fig. 7 is the acidic sample rate of recovery of hybridization silica gel material of the present invention and the variation diagram of wash-out pH;
Fig. 8 is the acidic sample rate of recovery of hybridization silica gel material of the present invention and the variation diagram of wash-out methanol concentration;
Fig. 9 is the adsorptive capacity of hybridization silica gel material and the variation diagram of loading volume of the modification of the present invention every milligram amphotericeledrolyte.
Embodiment
Below in conjunction with embodiment, the present invention will be further described.
Embodiment 1:
The synthetic route of the preparation of the hybridization silica gel material that amphotericeledrolyte is modified as shown in Figure 1, tetraethoxysilane (TEOS) and aminopropyl triethoxysilane (APTES) they are precursor molecule, with cetyl trimethylammonium bromide (CTAB) be template, with dehydrated alcohol for solvent, adopt sol-gel method to prepare the hybridization silica gel material (Fig. 1) containing amido in a kind of surface.This hybridization silica gel material with amido and the aldehyde radical of excessive glutaraldehyde react under the condition of pH8.0, generate C=N, make aldehyde radical on hybridisation silica gel surface bond, apply identical method, under the condition of pH8.0, the aldehyde radical of the glutaraldehyde the other end on hybridization silica gel material bonding and excessive amphotericeledrolyte amido react, the C=N of generation, this C=N is unstable, need use NaCNBH
3c=N is reduced into stable C-N(Fig. 1).
Concrete synthetic method is as follows: take 160mg cetyl trimethylammonium bromide (CTAB) in 50mL plastic centrifuge tube, add 2.24 mL tetraethoxysilanes (TEOS), 2.36 mL aminopropyl triethoxysilanes (APTES) and 4.35 mL dehydrated alcohols, vibrate with eddy mixer, water-bath subsequently 30 DEG C, until CTAB dissolves completely, mix with eddy mixer vibration after adding 0.64mL water again, in 40 DEG C of water-baths reaction 24h.After having reacted, by 5mL washed with methanol 2-3 time, wash away unreacted CTAB, then rinse 2-3 time with the 100mmol/L phosphoric acid salt that pH is 8.0, add again with the 100mmol/L phosphoric acid salt of pH8.0 dilute 10% glutaraldehyde, 90 DEG C reaction 0.5h, color can be observed and become brown; Rinse 2-3 time with the 100mmol/L phosphoric acid salt of pH8.0 again, add 0.625mL 10% amphotericeledrolyte and 5mg/mL NaCNBH
3, after 90 DEG C of reaction half an hour, with distilled water flushing 2-3 time, 60 DEG C to toast 10h stand-by.After the material of above-mentioned oven dry is ground, wait to load, scanning electron microscope as shown in Figure 2, particle is less than 10 μm (being 9.13*6.33 μm in Fig. 2) as seen from the figure, aperture nm level (368nm) is to μm level (being 1.70*0.87 μm in Fig. 2), the mesopore of nm level can increase specific surface area, and the through-hole of μm level makes it have good permeability.
Fig. 3 is the infrared spectrum of the hybridization silica gel material that amphotericeledrolyte is modified.2940cm
-1the acromion at place is the hydroxyl group absorption peak of typical carboxylic acid, 950 cm
-1for O-H out-of-plane deformation vibration, 1643 cm
-1for C=O stretching vibration, the modified upper carboxyl in illustrative material surface.1060 cm
-1for Si-O-Si stretching vibration, C-N stretching vibration is covered, 1542 cm
-1for N-H formation vibration, 790 cm
-1for N-H out-of-plane deformation vibration, illustrate that this material contains amido.
Embodiment 2:
Take the hybridization silica gel material 50mg that amphotericeledrolyte prepared by embodiment 1 is modified, under tape loaded 5 μm of apertures sieve plate 3mL column jecket in, insert after 20 μm of aperture upper sieve plates with vibrating bed concussion evenly, use presser-into-rod compacting.
Embodiment 3:
Quartz capillary is successively through dense HNO
3(10min), distilled water, HF(10min), distilled water, 1mol/L NaOH(12h), distilled water, 0.1mol/L HCl(1h), distilled water, after methyl alcohol process, quartz capillary column is placed in gas-chromatography stove, at the N of 120 DEG C
2flow down dry 3h, by 112 μ L tetraethoxysilanes (TEOS), 118 μ L aminopropyl triethoxysilanes (APTES), 215 μ L dehydrated alcohols, after 32 μ L water and 8mg cetyl trimethylammonium bromide (CTAB) fully mix, introduce in the good quartz capillary of pre-treatment through syringe, with silicon rubber by after sealing two ends, heat 40 DEG C of reactive polymeric 24 h, the material be polymerized is removed CTAB(30min through constant current syringe pump alcohol flushing), water and 100mmol/L phosphoric acid salt (pH 8.0) is used to rinse again respectively, then be continuously pumped into the 100mmol/L phosphoric acid salt (pH 8.0) containing 10% glutaraldehyde, 90 DEG C of reaction 0.5h, 30min is rinsed with phosphate buffered saline buffer, add containing 31 μ L 10% amphotericeledrolyte and 5mg/mL NaCNBH
3100mmol/L phosphoric acid salt (pH 8.0), after 90 DEG C of reduction reaction 0.5h, generate band many-NH
2with the hybridization silica gel material of many-COOH, then rinse with the phosphate buffered saline buffer of 100mmol/L, stand-by.
Embodiment 4:
For neutral and basic sample solution, loading pH condition is optimized.
Made the consolidating of embodiment 2 is adopted to get column extractor, respectively with 5mL methyl alcohol, the activation of 5.0mL water, vanillin food grade,1000.000000ine mesh (pka 7.78), methyl p-hydroxybenzoate (pka 8.31), ethyl p-hydroxybenzoate (pka 8.31), propylparaben (pka 8.23) and butyl p-hydroxybenzoate (pka 8.22) are dissolved in the hydrochloric acid buffer solution of pH 4.0,5.0,6.0,7.0 respectively, each sample concentration is 0.01mg/mL, loading 1mL, flow through with the flow velocity of 4-5mL/min and admittedly get column extractor, collect the sample flowed out, then analyze with HPLC.Liquid phase separation condition: 35% buffering salt (triethylamine 12.5mL, phosphoric acid 25.7mL, deionized water 1000mL are 2.0 by ammoniacal liquor adjust ph, cross 0.45 μm of filter membrane)-65% methyl alcohol; Sampling volume: 20 μ L; Determined wavelength is except vanillin food grade,1000.000000ine mesh, and all the other samples are 254nm, and vanillin food grade,1000.000000ine mesh is 230nm; Flow velocity 1mL/min; Chromatographic column: Inertsil ODS-SP, 5 μm, 150mm*4.6mm.The rate of recovery as shown in Figure 4, when pH is 6.0, the rate of recovery of five samples flowed out reaches minimum value and is respectively: 2.22%, 3.75%, 1.19%, 0.00%, 0.00%, and five sample recovery rates of the reservation namely on post reach maximum value and are respectively 97.78%, 96.25%, 98.81%, 100.00%, 100.00%.
Embodiment 5:
For neutral and basic sample solution, pH condition during wash-out is optimized.
Adopt the solid-phase extraction column that embodiment 2 is made, respectively with 5mL methyl alcohol, 5.0mL water activates, by vanillin food grade,1000.000000ine mesh (pka 7.78), methyl p-hydroxybenzoate (pka 8.31), ethyl p-hydroxybenzoate (pka 8.31), propylparaben (pka 8.23) and butyl p-hydroxybenzoate (pka 8.22) are dissolved in the buffered soln of pH 6.0, each sample concentration is 0.01mg/mL, loading 1mL, flow through with the flow velocity of 4-5mL/min and admittedly get column extractor, solid-phase extraction column is rinsed 3 times with the hydrochloric acid buffer solution of 3mL pH 6.0, subsequently, 1 is respectively with 2mL pH, 2, the hydrochloric acid buffer solution wash-out of 3, after collecting elutriant, analyze with HPLC again.Liquid phase separation condition: 35% buffering salt (triethylamine 12.5mL, phosphoric acid 25.7mL, deionized water 1000mL are 2.0 by ammoniacal liquor adjust ph, cross 0.45 μm of filter membrane)-65% methyl alcohol; Sampling volume: 20 μ L, determined wavelength is except vanillin food grade,1000.000000ine mesh, and all the other samples are 254nm, and vanillin food grade,1000.000000ine mesh is 230nm; Flow velocity 1mL/min; Chromatographic column: Inertsil ODS-SP, 5 μm, 150mm*4.6mm.As shown in Figure 5, as seen from the figure, during pH 1.0, the rate of recovery of five samples reaches maximum value to the rate of recovery, is respectively: 100.95%, 94.13%, 93.93%, 78.48%, 18.60%.
Embodiment 6:
For neutral and basic sample solution, the impact of methanol concentration during wash-out is investigated.
Adopt the solid-phase extraction column that embodiment 2 is made, respectively with 5mL methyl alcohol, 5.0mL water activates, by vanillin food grade,1000.000000ine mesh (pka 7.78), methyl p-hydroxybenzoate (pka 8.31), ethyl p-hydroxybenzoate (pka 8.31), propylparaben (pka 8.23) and butyl p-hydroxybenzoate (pka 8.22) are dissolved in the buffered soln of pH 6.0, each sample concentration is 0.01mg/mL, loading 1mL, flow through with the flow velocity of 4-5mL/min and admittedly get column extractor, solid-phase extraction column is rinsed 3 times with the hydrochloric acid buffer solution of 3mL pH 6.0, subsequently, with containing 0% respectively, 5%, 10%, 20%, 30%, 40%, the buffered soln wash-out of the pH 1.0 of 50% methyl alcohol, analyze with HPLC.Liquid phase separation condition: 35% buffering salt (triethylamine 12.5mL, phosphoric acid 25.7mL, deionized water 1000mL are 2.0 by ammoniacal liquor adjust ph, cross 0.45 μm of filter membrane)-65% methyl alcohol; Sampling volume: 20 μ L; Determined wavelength is except vanillin food grade,1000.000000ine mesh, and all the other samples are 254nm, and vanillin food grade,1000.000000ine mesh is 230nm; Flow velocity 1mL/min; Chromatographic column: Inertsil ODS-SP, 5 μm, 150mm*4.6mm.As shown in Figure 6, as seen from the figure, when elutriant contains 50% methyl alcohol, the rate of recovery reaches maximum value to the rate of recovery, is respectively 102.35%, 91.16%, 95.96%, 100.00% and 98.28%.
Embodiment 7:
For acidic sample, loading pH condition is optimized.
Adopt the solid-phase extraction column that embodiment 2 is made, respectively with 5mL methyl alcohol, the activation of 5.0mL water, soluble saccharin (pka 2.2), P-hydroxybenzoic acid (pka 4.6) are dissolved in the hydrochloric acid buffer solution of pH 5.0,6.0,7.0 respectively, each sample concentration is 0.01mg/mL, loading 1mL, flow through with the flow velocity of 4-5mL/min and admittedly get column extractor, collect the sample flowed out, then analyze with HPLC.The ammonium acetate of liquid phase separation condition: 0.02mol/L is 3.0 by formic acid adjust ph; Flow velocity 1.0mL/min; Chromatographic column: NuclEOsil-C18,5 μm, 250mm*4.6mm; Sampling volume: 20 μ L; Determined wavelength 230nm.All sample do not detected.Namely, under as above pH condition, soluble saccharin and P-hydroxybenzoic acid are retained on pillar by very strong.Due to when extracting neutral and basic sample solution, the pH of loading is 6.0.Therefore, conveniently processing sample, the pH for the loading of acidic sample also elects 6.0 as.
Embodiment 8:
For acidic sample, the pH condition of wash-out is optimized.
Adopt the solid-phase extraction column that embodiment 2 is made, respectively with 5mL methyl alcohol, the activation of 5.0mL water, soluble saccharin (pka 2.2), P-hydroxybenzoic acid (pka 4.6) are dissolved in the hydrochloric acid buffer solution of pH 6.0, each sample concentration is 0.01mg/mL, loading 1mL, flow through with the flow velocity of 4-5mL/min and admittedly get column extractor, rinse with the hydrochloric acid buffer solution of 3mL pH 6.0 again and admittedly get column extractor 3 times, subsequently, the hydrochloric acid buffer solution wash-out of 9,10,11 and 12 is respectively with 2mL pH, after collecting elutriant, then analyze with HPLC.The ammonium acetate of liquid phase separation condition: 0.02mol/L is 3.0 by formic acid adjust ph; Flow velocity 1.0mL/min; Chromatographic column: NuclEOsil-C18,5 μm, 250mm*4.6mm; Sampling volume: 20 μ L; Determined wavelength 230nm.As seen from Figure 7, when pH is 11, the rate of recovery of soluble saccharin and P-hydroxybenzoic acid reaches maximum value.Therefore, the pH of wash-out elects 11 as.
Embodiment 9:
For acidic sample, the concentration of organic solvent in elutriant is investigated.
Adopt the solid-phase extraction column that embodiment 2 is made, respectively with 5mL methyl alcohol, 5.0mL water activates, by soluble saccharin (pka 2.2), P-hydroxybenzoic acid (pka 4.6) is dissolved in the hydrochloric acid buffer solution of pH 6.0, each sample concentration is 0.01mg/mL, loading 1mL, flow through with the flow velocity of 4-5mL/min and admittedly get column extractor, rinse with the hydrochloric acid buffer solution of 3mL pH 6.0 again and admittedly get column extractor 3 times, subsequently, with containing 0% respectively, 5%, 10%, 20%, 40%, the pH of 60% and 80% methyl alcohol is 11 hydrochloric acid buffer solution wash-outs, volume is 2mL, after collecting elutriant, analyze with HPLC again.The ammonium acetate of liquid phase separation condition: 0.02mol/L is 3.0 by formic acid adjust ph; Flow velocity 1.0mL/min; Chromatographic column: NuclEOsil-C18,5 μm, 250mm*4.6mm; Sampling volume: 20 μ L; Determined wavelength 230nm.As shown in Figure 8, when methanol content is 40%, the rate of recovery of two samples is maximum, is respectively 83.49% and 85.22% for the rate of recovery.
Embodiment 10:
For neutral and basic sample solution, hybridization silica gel material circulation ratio in Solid-Phase Extraction that amphotericeledrolyte is modified is investigated.
Adopt the solid-phase extraction column that embodiment 2 is made, respectively with 5mL methyl alcohol, 5.0mL water activates, by vanillin food grade,1000.000000ine mesh (pka 7.78), methyl p-hydroxybenzoate (pka 8.31), ethyl p-hydroxybenzoate (pka 8.31), propylparaben (pka 8.23) and butyl p-hydroxybenzoate (pka 8.22) are dissolved in the buffered soln of pH 6.0, each sample concentration is 0.01mg/mL, loading 1mL, flow through with the flow velocity of 4-5mL/min and admittedly get column extractor, rinse with the hydrochloric acid buffer solution of 3mL pH 6.0 and admittedly get column extractor 3 times, subsequently, with the buffered soln wash-out of the pH 1.0 of 50% methyl alcohol, analyze with HPLC.Liquid phase separation condition: 35% buffering salt (triethylamine 12.5mL, phosphoric acid 25.7mL, deionized water 1000mL are 2.0 by ammoniacal liquor adjust ph, cross 0.45 μm of filter membrane)-65% methyl alcohol; Sampling volume: 20 μ L; Determined wavelength is except vanillin food grade,1000.000000ine mesh, and all the other samples are 254nm, and vanillin food grade,1000.000000ine mesh is 230nm; Flow velocity 1mL/min; Chromatographic column: Inertsil ODS-SP, 5 μm, 150mm*4.6mm.Mensuration 5 times altogether, average recovery rate is: 102.35%, 91.16%, 95.96%, 100.00%, 98.28%, and relative standard deviation is respectively: 4.42%, 4.11%, 4.67%, 4.63% and 1.60%.
Embodiment 11:
For neutral and basic sample solution, the adsorptive capacity of the hybridization silica gel material of every milligram of amphotericeledrolyte modification as shown in Figure 9, the visible increase along with loading volume, the i.e. increase of applied sample amount, the adsorptive capacity of every milligram of material increases, when loading volume is 4 mL, the adsorptive capacity of every milligram of material reaches maximum value, reaches 0.6-1.5 μ g/mg.
Claims (3)
1. the hybridization silica gel material that amphotericeledrolyte is modified makes the method for solid-phase extraction column, its feature comprises the following steps: take the hybridization silica gel material that 50mg amphotericeledrolyte is modified, under tape loaded 5 μm of apertures sieve plate 3mL column jecket in, even with vibrating bed concussion after inserting 20 μm of aperture upper sieve plates, use presser-into-rod compacting; The hybridization silica gel material that described amphotericeledrolyte is modified is the ampholine that bonding contains amido and carboxyl on hybridisation silica gel side chain, and the chemical structural formula elementary cell of the hybridization silica gel material that described amphotericeledrolyte is modified is:
。
2. the solid phase extraction method of the solid-phase extraction column that the hybridization silica gel material that amphotericeledrolyte according to claim 1 is modified is made, its feature comprises the following steps: by the solid-phase extraction column of hybridization silica gel material installed, respectively with 5mL methyl alcohol, the activation of 5.0mL water; Vanillin food grade,1000.000000ine mesh, methyl p-hydroxybenzoate, ethyl p-hydroxybenzoate, propylparaben and butyl p-hydroxybenzoate are dissolved in the hydrochloric acid buffer solution of pH 6.0, each sample concentration is 0.01mg/mL, loading 1mL, flow through solid-phase extraction column with the flow velocity of 4-5mL/min, complete loading; Subsequently, with the buffered soln wash-out of the pH 1.0 containing 50% methyl alcohol, analyze with HPLC, the rate of recovery is respectively 102.35%, 91.16%, 95.96%, 100.00% and 98.28%.
3. the solid phase extraction method of the solid-phase extraction column that the hybridization silica gel material that amphotericeledrolyte according to claim 1 is modified is made, its feature comprises the following steps: by the solid-phase extraction column of hybridization silica gel material assembled, respectively with 5mL methyl alcohol, the activation of 5.0mL water; Be dissolved in the buffered soln of pH6.0 by soluble saccharin and P-hydroxybenzoic acid, each sample concentration is 0.01mg/mL, loading 1mL, flows through solid-phase extraction column, complete loading with the flow velocity of 4-5mL/min; Subsequently, with the buffered soln wash-out of the pH11.0 containing 40% methyl alcohol, analyze with HPLC, the rate of recovery is respectively 83.49% and 85.22%.
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1831526A (en) * | 2005-03-07 | 2006-09-13 | 中国科学院大连化学物理研究所 | Gradient separation material |
| CN102029147A (en) * | 2009-09-25 | 2011-04-27 | 中国科学院大连化学物理研究所 | Zwitter-ion chromatography stationary phase and preparation method thereof |
Non-Patent Citations (4)
| Title |
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| Fast preparation of monolithic immobilized pH gradient column by photopolymerization and photografting techniques for isoelectric focusing separation of proteins;Yu Liang等,;《Electrophoresis》;20110922;第2911-2914页, 尤其是第2912页图1 * |
| Hybrid organic–inorganic silica monolith with hydrophobic/strong cation-exchange functional groups as a sorbent for micro-solid phase extraction;Ming-Ming Zheng等,;《Journal of Chromatography A》;20090906;第63-72页 * |
| Organic-Inorganic Hybrid Silica Monolith Based Immobilized Trypsin Reactor with High Enzymatic Activity;Junfeng Ma等,;《Anal. Chem.》;20080312;第2949-2956页, 尤其是第2950页右栏第3-4段以及第2951页图1 * |
| Repeatedly usable immobilized pH gradient in a monolithic capillary column;Chun Yang等,;《Electrophoresis》;20040717;第1729-1734页, 尤其是第1730页2.2部分和第1731页图1 * |
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