CN105148559B - Preparation of embedded attapulgite capillary monolithic column and method for using capillary monolithic column for solid phase micro extraction - Google Patents
Preparation of embedded attapulgite capillary monolithic column and method for using capillary monolithic column for solid phase micro extraction Download PDFInfo
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Abstract
The invention provides a preparation method of an embedded attapulgite capillary monolithic column. The method comprises the following steps of mixing acidified attapulgite and an organic polymer solution at a mass ratio being 1:100 to 5:100; performing magnetic stirring for 1 to 5 hours at the normal temperature so that the acidified attapulgite is completely dispersed; then, injecting the material into a quartz capillary treated by gamma-2-methyl propyl trimethoxy silane; sealing the material; then putting the materials into a constant-temperature water bath pot for reaction for 16 to 24h at 60 to 85 DEG C; after the reaction is completed, using acetonitrile and water for flushing; preparing the material for use. The natural attapulgite nanometer materials are embedded into an organic polymer monolithic material for the first time; the embedded attapulgite capillary monolithic column is prepared. The preparation method has the advantages that the simplicity is realized; the cost is low; the reaction condition can be easily controlled; the prepared embedded attapulgite capillary monolithic column has higher mechanical intensity and higher permeability; when the prepared embedded attapulgite capillary monolithic column is used as an adsorbing agent to be applied to solid micro extraction, the advantages of great adsorption volume, high recovery yield, good reproducibility, low detection limit and the like are realized. The preparation method is applicable to the sample pretreatment of polar small-molecular compounds.
Description
Technical field
The present invention relates to chromatography Sample Pretreatment Technique Used, particularly a kind of capillary monolithic column of embedding attapulgite
Preparation and solid phase micro-extraction method.
Background technology
In recent years, have that preparation is simple, permeability is good due to Organic Polymer Monolithic Columns, ph range width, modification side
Just so as to obtain extensive concern in sample pretreatment field many advantages, such as fast with mass transfer velocity.But, this kind of material is micro-
Tens square metres of action sites between every gram, and sample are less so as to specific surface area only has for the shortage of pore structure, and column capacity is not
Foot, leads to it to be less than granular filler even silica gel integral material to the adsorption capacity of small molecule.
Nano material crystal grain is little, specific surface area big so as to create the quantum size effect that bulk material do not have with
Skin effect etc..Therefore, by nano material embedding or modify on organic polymer integral material can with increasing specific surface area,
It is a kind of to effectively improve small molecule adsorption capacity and the method for accumulation ability.Gama-alumina is embedded in poly- (n- isopropyl by li etc.
Acrylamide-n, n '-methylene-bisacrylamide) in integral post, the application of solid-phase microextraction effectively raises pairing
Become adsorbance (li, the w. of food dye; zhou, x.; tong, s.; jia, q.talanta2013,105, 386-
392).Wang etc. is prepared for poly- (methacrylic acid-dimethyl ethyl-CNT) integral post, to triazines weeding
Agent has carried out selective enrichment, and lowest detectable limit reaches 0.06～0.46 ng/ml(wang, x.; li, x.; li, z.;
zhang, y.; bai, y.; liu, h.anal. chem.2014,86, 4739-4747).Tong etc. is by Graphene bag
It is embedded in poly- (butyl methacrylate-dimethyl ethyl) integral post, improve the accumulation ability to glucocorticoid
(tong, s.; liu, q.; li, y.; zhou, w.; jia, q.; duan, t.j. chromatogr. a2012,1253, 22-31).
Attapulgite is that a kind of have nanochannel structure, large specific surface area, cheap natural nano structure ore deposit
Thing material, preferable molecular formula is: [(oh2)4(mg, al, fe)5(oh).2si8o20]·4h2o.Attapulgite crystal table
Face and inside containing the hydroxyl structure such as substantial amounts of silicone hydroxyl, magnesium hydroxyl, aluminum hydroxyl and are adsorbed water, are combined water, three kinds of water of constitution water
Part is so as to surface assumes stronger hydrophilic.
Content of the invention
The technical problem to be solved in the present invention is to provide a kind of capillary monolithic column of embedding attapulgite, for ring third
Amine piperazine and the solid-phase microextraction of tripolycyanamide.
The present invention employs the following technical solutions and is attained in that
The preparation method of the capillary monolithic column of embedding attapulgite, comprises the following steps: 1) is acidified the system of attapulgite
Preparation Method, by attapulgite mill pulverizing, be sized to below 200 mesh, be subsequently adding concentration of hydrochloric acid 0.5～12 mol/l, concavo-convex
The ratio of rod soil and hydrochloric acid is 1:2～1:30 g/ml, and 20～85 ° of c for the treatment of temperature, process time 0.5～7 h use distilled water
Washing, filter after, 60～120 ° of c of baking oven dry 5～10 h, obtain the attapulgite being acidified after milling；
2) preparation method of organic polymer soln is: using 1- sulfonic acid butyl -3- vinyl imidazole inner salt and acryloyl
Amine is as function monomer, n, n '-methylene-bisacrylamide be cross-linking agent, Methanamide, dimethyl sulfoxide, peg-8,000 He
Peg-10,000 is porogen, and azodiisobutyronitrile is initiator, stand-by after being sufficiently mixed；
3) described acidifying attapulgite is mixed with the mass ratio of 1:100～5:100 with described organic polymer soln,
Room temperature magnetic agitation 1～5 h, injects γ -2- methacryloxypropyl trimethoxy after so that acidifying attapulgite is completely dispersed
In the quartz capillary of silane treatment, it is placed in 60～85 ° of c in thermostat water bath after sealing and reacts 16～24 h, question response completes
Acetonitrile and water is used to rinse afterwards again, stand-by.
The method that the capillary monolithic column of embedding attapulgite is used for solid-phase microextraction cyclopropylamine piperazine: attapulgite will be embedded
Capillary monolithic column first rinsed with 95%～100% acetonitrile, by cyclopropylamine piperazine with the flow velocity loading 0.5 of 2～10 μ l/min～
After 2.5 min, adopt 0%～50% acetonitrile with flow velocity eluting 20～40 min of 1～2 μ l/min, with height after eluent is collected
Effect liquid phase chromatogram detects.
The method that the capillary monolithic column of embedding attapulgite is used for solid-phase microextraction tripolycyanamide: attapulgite will be embedded
Capillary monolithic column first with 95%～100% acetonitrile rinse, by tripolycyanamide with the flow velocity loading 10～50 of 2～10 μ l/min
After min, adopt 0%～50% acetonitrile with flow velocity eluting 20～40 min of 1～2 μ l/min, after eluent is collected, use efficient liquid
Phase chromatograph detects.
Advantages of the present invention and good effect are: first natural attapulgite nanometer material is embedded in organic polymer whole
In body material, the capillary monolithic column of preparation embedding attapulgite, this preparation method is simple, and with low cost, reaction condition is easy
Control, the capillary monolithic column of prepared embedding attapulgite has stronger mechanical strength and higher permeability, as suction
Attached dose is applied to solid-phase microextraction, has that adsorption capacity is big, the response rate is high, the low advantage of favorable reproducibility, detection limit is it is adaptable to pole
The sample pretreatment of property micromolecular compound.The present invention is according to the hydrophilic of attapulgite lattice structure cationic and replaceable
Property, crystal is in raphioid fiber structure, makes embedding attapulgite capillary monolithic column using attapulgite, as solid-phase microextraction
Adsorbent is it is achieved that the selective enrichment of milk powder medium ring propylamine dihydrochloride and tripolycyanamide, whole with the capillary tube not embedding attapulgite
Scapus is compared, and this material improves 6.4 times to the adsorbance of tripolycyanamide.
Brief description
Fig. 1 is the breakthrough curve figure of capillary monolithic column.A () is the embedding mass ratio of embodiment 1 preparation is 5% attapulgite
The breakthrough curve figure of the capillary monolithic column of soil；B () is the capillary tube that embedding mass ratio prepared by embodiment 2 is 3% attapulgite
The breakthrough curve figure of integral post；C () is the capillary monolithic column that embedding mass ratio prepared by embodiment 3 is 1.6% attapulgite
Breakthrough curve figure；D () is the breakthrough curve figure of the capillary monolithic column not embedding attapulgite of embodiment 4 preparation；When () is dead e
Between mensure: the capillary monolithic column not embedding attapulgite that 0.1 mg/ml toluene is prepared by embodiment 4；
The scanning electron microscope (SEM) photograph (Fig. 2 a) of attapulgite and energy spectrum diagram (Fig. 2 b) that Fig. 2 is processed for step (2)；
The scanning electron microscope (SEM) photograph (Fig. 3 a) of the capillary monolithic column not embedding attapulgite of Fig. 3 embodiment 4 preparation and energy
Spectrogram (Fig. 3 b)；
The embedding mass ratio of Fig. 4 embodiment 1 preparation is the scanning electron microscope (SEM) photograph (figure of the capillary monolithic column of 5% attapulgite
4a) and energy spectrum diagram (Fig. 4 b)；
Fig. 5 is infrared spectrogram.A attapulgite that () step (2) is processed；B prepared by () embodiment 4 does not embed attapulgite
The capillary monolithic column of soil；C the embedding mass ratio of () embodiment 1 preparation is the capillary monolithic column of 5% attapulgite.
Specific embodiment
Attapulgite is commercially available crystalloid hydrous magnesium aluminosilicate clays mineral, and embodiment raw materials are that commercially available chemistry is pure
Or analysis pure chemistry reagent；Mobile phase is acetonitrile and distilled water (v/v) is prepared；Quartz capillary 200 μm of column internal diameter of entirety,
Long capillary tube 25 cm measuring for breakthrough curve, for the long capillary tube 10 of cyclopropylamine piperazine and tripolycyanamide solid-phase microextraction
cm.
Prepare the capillary monolithic column of embedding attapulgite according to following steps.
(1) pretreatment in quartz capillary
First by quartz capillary successively with 0.5 mol/l hydrochloric acid, distilled water, 0.5 mol/l sodium hydroxide, distilled water and
Methanol rinses capillary tube, is dried up with nitrogen；γ -2- methyl allyl acyloxypropyl trimethoxysilane by volume ratio 1:1
Methanol solution be injected in above-mentioned capillary tube；Standing and reacting 12 h at room temperature；Subsequently, rinsed with methanol, in the nitrogen of 70 ° of c
1 h is dried standby under air-flow.
(2) acidification of attapulgite
By attapulgite mill pulverizing, be sized to below 200 mesh, be subsequently adding concentration of hydrochloric acid 4 mol/l, attapulgite and
The ratio of hydrochloric acid be 1:10 g/ml, 75 ° of c for the treatment of temperature, process time 4 h, with distilled water wash, filter after, 110 ° of baking oven
C dries 8 h, obtains the attapulgite being acidified after milling.
(3) organic polymer soln is prepared
The 1- sulfonic acid butyl -3- vinyl imidazole inner salt of 167 mg and the vibration of 1934 mg Methanamides are mixed, is subsequently added
50 mg acrylamides vibrations mix, and add 100 mg n, n '-methylene-bisacrylamide, 967 mg dimethyl sulfoxide,
106 mg peg-8,000,192 mg peg-10,000 and 3.2 mg azodiisobutyronitriles, mix homogeneously.
(4) synthetic in quartz capillary column
Embodiment 1: weigh organic polymer soln 2 g that step (3) is prepared, it is recessed that addition 0.1 g step (2) was processed
Convex rod soil, at room temperature, magnetic agitation 3 h, so that attapulgite is dispersed in organic polymer soln, subsequently, use nitrogen
Deaerate 5 min, in the capillary tube that implantation step (1) was processed, stoppers capillary tube two ends with silicone rubber, in 75 ° of c constant temperature water baths
It is cooled to room temperature after middle heating 20 h, obtain the embedding attapulgite that attapulgite is 5% with organic polymer soln mass ratio
Capillary monolithic column.
Embodiment 2: weigh organic polymer soln 2 g that step (3) is prepared, add 0.06 g step (2) to process
Attapulgite, at room temperature, magnetic agitation 3 h, so that attapulgite is dispersed in organic polymer soln, subsequently, use nitrogen
QI prostration gas 5 min, in the capillary tube that implantation step (1) was processed, stoppers capillary tube two ends with silicone rubber, permanent in 75 ° of c water-baths
Warming middle-JIAO is cooled to room temperature after heating 20 h, obtains the embedding attapulgite that attapulgite is 3% with organic polymer soln mass ratio
Capillary monolithic column.
Embodiment 3: weigh organic polymer soln 2 g that step (3) is prepared, add 0.032 g step (2) to process
Attapulgite, at room temperature, magnetic agitation 3 h, so that attapulgite is dispersed in organic polymer soln, subsequently, use nitrogen
QI prostration gas 5 min, in the capillary tube that implantation step (1) was processed, stoppers capillary tube two ends with silicone rubber, permanent in 75 ° of c water-baths
Warming middle-JIAO is cooled to room temperature after heating 20 h, obtains the embedding attapulgite that attapulgite is 1.6% with organic polymer soln mass ratio
The capillary monolithic column of soil.
Embodiment 4: as a comparison, the organic polymer soln that step (3) is prepared, with nitrogen degassing 5 min, implantation step
(1) in the capillary tube processing, stopper capillary tube two ends with silicone rubber, be cooled to after heating 20 h in 75 ° of c constant temperature water baths
Room temperature, is not embedded the capillary monolithic column of attapulgite.
The breakthrough curve figure of the capillary monolithic column prepared by embodiment 1,2,3,4 is respectively as Fig. 1 (a) and (b), (c), (d)
Shown, all with 0.1 mg/ml tripolycyanamide (being dissolved in 95% acetonitrile) as sample, capillary tube is passed through with the flow velocity of 2.4 μ l/min whole
Scapus.E () passes through the attapulgite that do not embed prepared by embodiment 4 with 0.1 mg/ml toluene (being dissolved in 95% acetonitrile) for sample
Capillary monolithic column, measures the dead time.Detection wavelength is 214 nm.It will be seen from figure 1 that with attapulgite mass fraction
Increase, tripolycyanamide increased by time of capillary monolithic column, and that is, adsorbance is with the increase of attapulgite mass fraction
And increase.By calculate it can be deduced that attapulgite and organic polymer soln mass ratio be 0%, 1.6%, 3% and 5% absorption
Amount is respectively 48,190,238 and 308 μ g/ml.Embedding attapulgite capillary monolithic column maximal absorptive capacity be do not embed recessed
6.4 times of the capillary monolithic column of convex rod soil.
The scanning electron microscope (SEM) photograph of the attapulgite that Fig. 2 is processed for step (2) is it can be seen that acidifying attapulgite assumes fiber
Shape, length is less than 1 μm, as can be seen that attapulgite contains fe, al, mg, si and o element from corresponding power spectrum.Fig. 3 is real
Apply the scanning electron microscope (SEM) photograph of the capillary monolithic column not embedding attapulgite of example 4 preparation, it can be seen that not embedding concavo-convex
The capillary monolithic column of rod soil contains loose structure, and about 0.5～2.0 μm of aperture can be seen that whole from corresponding power spectrum
Body material contains n, s and o element.Fig. 4 is the capillary monolithic column that embedding mass ratio prepared by embodiment 1 is 5% attapulgite
Scanning electron microscope (SEM) photograph, it can be seen that attapulgite is preferably embedded in integral material, permissible from corresponding power spectrum
Find out, the capillary monolithic column of embedding attapulgite contains fe, al, mg, si, o, n and s element, further illustrates attapulgite
Preferably it is embedded in integral material.
Fig. 5 is the infrared spectrogram of several different materials.1680 cm-1Stretching vibration for c=o, 1455 cm-1For imidazoles
The stretching vibration of ring, above equal can be in embodiment 1(c) and embodiment 4(b) find in the capillary monolithic column prepared.Additionally,
474 cm−1With 800 cm−1Be respectively si o si and al o si stretching vibration, above equal can embodiment 1 preparation
Find in the attapulgite (a) that capillary monolithic column (c) and step (2) are processed.Therefore, the capillary tube of embedding attapulgite is overall
Post comprises the characteristic peak of integral material and attapulgite, further illustrates attapulgite and is preferably embedded in integral material
In.
Concrete application embodiment:
Embodiment 5: the capillary monolithic column of the embedding attapulgite prepared by checking embodiment 1 is consolidated to cyclopropylamine piperazine
Phase extraction performance, with the capillary monolithic column of prepared embedding attapulgite as adsorbent, using high performance liquid chromatography pair
Milk powder is analyzed.
The preparation of milk powder: 10 g milk powder add 30 ml acetonitriles, for precipitating proteins, vibrates 35 min, and subsequent 15,000
G is centrifuged 10 min, takes supernatant to be diluted with water to containing 95% acetonitrile, after 0.45 μm of filter membrane, adds respective volume
The standard solution of 0.1 mg/ml cyclopropylamine piperazine, makes concentration be respectively 80,400 and 1600 ng/ml.
Extraction conditionss: using the capillary monolithic column prepared by embodiment 1, first rinsed with 95% acetonitrile, with 4 μ l/min's
After flow velocity loading 1.25 min, adopt 20% acetonitrile with flow velocity eluting 20 min of 2 μ l/min, with efficiently after eluent is collected
Liquid chromatographic detection.
Chromatographiccondition: analytical column is Yi Lite hypersil nh2(4.6 × 150 mm, 5 μm), mobile phase is
90% acetonitrile, flow velocity 0.8 ml/min, sample introduction 20 μ l, 30 ° of c of column temperature, Detection wavelength 214 nm.
Result shows, when in milk powder extracting solution, when the spiked levels of cyclopropylamine piperazine are 80,400 and 1600 ng/ml, reclaims
Rate is respectively 94.51%, 95.85% and 96.56%, rsds and is respectively 7.6%, 4.2% and 4.5%, and lowest detectable limit reaches 21.1
Ng/ml, illustrates that the method is suitable for the analysis of milk powder medium ring propylamine dihydrochloride.
Embodiment 6: the capillary monolithic column of the embedding attapulgite prepared by checking embodiment 1 is consolidated to tripolycyanamide
Phase extraction performance, with the capillary monolithic column of prepared embedding attapulgite as adsorbent, using high performance liquid chromatography pair
Milk powder is analyzed.
The preparation of milk powder: 10 g milk powder add 30 ml acetonitriles, for precipitating proteins, vibrates 35 min, and subsequent 15,000
G is centrifuged 10 min, takes supernatant to be diluted with water to containing 95% acetonitrile, after 0.45 μm of filter membrane, adds respective volume
The standard solution of 0.1 mg/ml tripolycyanamide, makes concentration be respectively 10,50 and 200 ng/ml.
Extraction conditionss: using the capillary monolithic column prepared by embodiment 1, first rinsed with 95% acetonitrile, with 4 μ l/min's
After flow velocity loading 25 min, adopt 20% acetonitrile with flow velocity eluting 20 min of 2 μ l/min, after eluent is collected, use efficient liquid
Phase chromatograph detects.
Chromatographiccondition is with embodiment 5.
Result shows, when in milk powder extracting solution, when the spiked levels of tripolycyanamide are 10,50 and 200 ng/ml, the response rate
It is respectively 109.92%, 100.46% and 97.92%, rsds and is respectively 1.4%, 1.6% and 2.6%, lowest detectable limit reaches 0.3 ng/
Ml, illustrates that the method is suitable for the analysis of tripolycyanamide in milk powder.
Claims (3)
1. the preparation method of the capillary monolithic column of embedding attapulgite, its feature comprises the following steps: 1) is acidified attapulgite
Preparation method be: by attapulgite mill pulverizing, be sized to below 200 mesh, be subsequently adding concentration of hydrochloric acid 0.5～12 mol/
The ratio of l, attapulgite and hydrochloric acid is 1:2～1:30 g/ml, and 20～85 ° of c for the treatment of temperature, process time 0.5～7 h use
Distilled water wash, filter after, 60～120 ° of c of baking oven dry 5～10 h, obtain the attapulgite being acidified after milling；
2) manufacture method of organic polymer soln is: is made using 1- sulfonic acid butyl -3- vinyl imidazole inner salt and acrylamide
For function monomer, n, n '-methylene-bisacrylamide be cross-linking agent, Methanamide, dimethyl sulfoxide, peg-8,000 and peg-10,
000 is porogen, and azodiisobutyronitrile is initiator, stand-by after being sufficiently mixed；
3) described acidifying attapulgite is mixed with the mass ratio of 1:100～5:100 with described organic polymer soln, room temperature
Stirring 1～5 h, makes acidifying attapulgite inject after being completely dispersed at through γ -2- methyl allyl acyloxypropyl trimethoxysilane
In the quartz capillary of reason, it is placed in 60～85 ° of c in thermostat water bath after sealing and reacts 16～24 h, use after the completion of question response again
Acetonitrile and water rinse, stand-by.
2. the capillary monolithic column of the embedding attapulgite that method is made according to claim 1 is used for solid-phase microextraction ring third
The method of amine piperazine it is characterised in that: the capillary monolithic column of embedding attapulgite is first used 95%～100% acetonitrile flushing, by ring
After propylamine dihydrochloride is with flow velocity loading 0.5～2.5 min of 2～10 μ l/min, adopt 0%～50% acetonitrile with the stream of 1～2 μ l/min
Fast eluting 20～40 min, uses high performance liquid chromatography detection after eluent is collected.
3. the capillary monolithic column of the embedding attapulgite that method is made according to claim 1 is used for solid-phase microextraction trimerization
The method of cyanamide it is characterised in that: the capillary monolithic column of embedding attapulgite is first used 95%～100% acetonitrile flushing, by three
After poly cyanamid is with flow velocity loading 10～50 min of 2～10 μ l/min, adopt 0%～50% acetonitrile with the flow velocity of 1～2 μ l/min
Eluting 20～40 min, uses high performance liquid chromatography detection after eluent is collected.
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| CN107684905B (en) * | 2017-09-20 | 2020-11-03 | 宁波工程学院 | Preparation method of organic-inorganic hybrid monolithic column based on attapulgite and application of organic-inorganic hybrid monolithic column in separation |
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