CN105921116B - Cation with immixture pattern exchanges Solid Phase Extraction material and its preparation method and application - Google Patents
Cation with immixture pattern exchanges Solid Phase Extraction material and its preparation method and application Download PDFInfo
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Abstract
A kind of cation exchange Solid Phase Extraction material and its preparation method and application with immixture pattern, it is characterised in that：The preparation method of the material is as follows：It is to be reacted to generate mercaptopropyltriethoxysilane SiClx glue in toluene environment with 3 mercaptopropyltriethoxysilanes by the spherical porous silica gel after activating（Sil‑MPS）, the mercaptopropyltriethoxysilane SiClx glue（Sil‑MPS）Again with 1 benzyl of bromination, 3 allyl benzene benzimidazole salt, allyl benzene sodium sulfonate is added in acetonitrile solvent jointly; add catalyst azodiisobutyronitrile; under nitrogen protection; it is reacted; filtering; it respectively washed once with toluene, methanol, water and acetone successively, it is dry to exchange Solid Phase Extraction material --- benzimidazole ionic liquid Solid Phase Extraction material to get the cation with immixture pattern.The material is applied to the highly polar compound of separation and concentration, interference can be effectively removed, isolate and purify effect obviously.
Description
Technical field
The invention belongs to technical field of chemical detection, and in particular to a kind of cation exchange with immixture pattern is solid
Phase fiber material（Benzimidazole ionic liquid Solid Phase Extraction material）, preparation method and in the highly polar compound of separation and concentration
Application.
Background technology
Solid Phase Extraction（Solid-Phase Extraction, abbreviation SPE）It is that developed recently gets up a kind of sample pretreatment
Technology is combined and is developed by liquid-solid extraction and column liquid chromatographic technology, is mainly used for micro in complex sample or trace mesh
Enrichment and the purification etc. for marking compound, can relatively improve the rate of recovery of analyte, more effectively compared with traditional liquid-liquid extraction method
Analyte is detached with interfering component, reduce sample pretreatment process, it is easy to operate, time saving, laborsaving.Currently, Solid Phase Extraction
Technology has been widely used in the fields such as medicine, food, environment, commodity inspection, chemical industry.
Solid phase extraction techniques are using solid-phase adsorbent to the difference of heterogeneity adsorption capacity in fluid sample and by target
The technology that object is detached with chaff interferent, core are solid phase extraction fillers, and suitable Solid Phase Extraction is selected according to different objects
Material can efficiently, quickly target analytes are detached and are enriched with.Currently, traditional Solid Phase Extraction material includes silica gel
Host material is bonded octadecyl, the groups such as octyl and the C18 Solid Phase Extraction material and C8 Solid Phase Extraction constituted that is, on silica gel
Material is mainly based upon hydrophobic effect and low pole and nonpolar target analytes is detached and be enriched with.With life
More and more important, traditional C18 and C8 are analyzed in science and pharmaceutical chemical development, the separation for highly polar charging cpd
Solid Phase Extraction material in this kind of compound of separation and concentration, there are active forces it is single, bioaccumulation efficiency is poor the problems such as, it would therefore be highly desirable to open
The Solid Phase Extraction material of sending out new improves the accumulation ability to polar compound.In recent years, in conjunction with reverse phase is hydrophobic and ion exchange
The mixed mode solid-phase extraction column (MMC) of retention mechanism is effectively maintained and selects because that can provide polarity charged analyte
Property and obtained faster development.Currently, having the solid-phase extraction column of the immixture pattern of some commercializations in the market, such as
Oasis MCX and ProElut PXC etc., but that all there is prices is high, the shortcomings of cannot reusing for this kind of Solid Phase Extraction material.
Therefore, simple, the practical Solid Phase Extraction material of exploitation preparation method, specificity and efficiency to improve separation and analysis method are
Very necessary.
Invention content
The purpose of the present invention is based on above-mentioned prior art situation and a kind of sun with immixture pattern for providing
Ion Exchange Solid Phase fiber material（Benzimidazole ionic liquid Solid Phase Extraction material）, which can improve polar compound
Separation and bioaccumulation efficiency further relate to π-π effects, pi-electron transfer other than with hydrophobic and cationic exchange interaction mechanism
Deng, complex sample separation analysis in have potential application value.
The purpose of the present invention is achieved through the following technical solutions：
A kind of cation exchange Solid Phase Extraction material with immixture pattern, specifically a kind of benzimidazole ionic liquid
Body Solid Phase Extraction material, structural formula I are：
Preparation method is as follows：It is by spherical porous silica gel and the 3- mercaptopropyltriethoxysilanes after activating in toluene environment
Middle reaction generates mercaptopropyltriethoxysilane SiClx glue（Sil-MPS）, the mercaptopropyltriethoxysilane SiClx glue（Sil-
MPS）Again with bromination 1- benzyl -3- allyl benzenes benzimidazole salt, allyl benzene sodium sulfonate is added in acetonitrile solvent jointly, then
Catalyst azodiisobutyronitrile is added, under nitrogen protection, is reacted, filters, is respectively washed with toluene, methanol, water and acetone successively
It washs once, it is dry to exchange Solid Phase Extraction material --- benzimidazole ionic liquid to get the cation with immixture pattern
Solid Phase Extraction material.
Synthetic route is as follows
Specific preparation process is as follows：
（1）Prepare activated silica gel：
By spherical porous silica gel（40-75 μm of grain size, specific surface area are 480 m2/g）Immerse the hydrochloric acid of volumetric concentration 10%
In, impregnate 6-8h, stir the lower 14-16h that flows back, remove metal ion, filtered with G5 sand core funnels, rinsed repeatedly with redistilled water to
Neutrality is washed 2-3 times with methanol, acetone successively, and 6-8h is dried in vacuo at 120 DEG C, is obtained to surface and is uniformly distributed the activation of hydroxyl
Silica gel；
（2）Prepare mercaptopropyltriethoxysilane SiClx glue：
3- mercaptopropyltriethoxysilanes are mixed with dry toluene, activation silicon is added under 15-25r/m magnetic agitations
Glue, 3- mercaptopropyltriethoxysilanes, dry toluene and the proportionate relationship of activated silica gel three of addition are 1 ml:5-8 ml:
0.3-0.6 g, and 110 DEG C are warming up to, it flows back under nitrogen protection for 24 hours；Then use G5 sand core funnels filter, successively use methanol,
Redistilled water, acetone wash and are dried in vacuo 10-12h at each 1-2 times, 50-60 DEG C, obtain mercaptopropyltriethoxysilane SiClx glue
（Sil-MPS）；
（3）The preparation of benzimidazole ionic liquid Solid Phase Extraction material
Preparation method is：By bromination 1- benzyl -3- allyl benzenes benzimidazole salt, to allyl benzene sodium sulfonate, mercapto propyl three
Ethoxysilane SiClx glue is added in acetonitrile solvent, adds catalyst azodiisobutyronitrile, the bromination 1- benzyls -3- of addition
Allyl benzene benzimidazole salt, to allyl benzene sodium sulfonate, mercaptopropyltriethoxysilane SiClx glue, acetonitrile and azodiisobutyronitrile
Proportionate relationship be 1g: 1-1.3g: 1.7-2g: 45-50ml:0.1-0.15 g, under nitrogen protection, in the catalysis of catalyst
Lower 60 DEG C of reactions 24-26h, filtering respectively washed once with toluene, methanol, water and acetone, 10- are dried in vacuo at 60 DEG C successively
12h is to get benzimidazole ionic liquid Solid Phase Extraction material.
The synthetic method of bromination 1- benzyl -3- allyl benzene benzimidazole salts is as follows：
It is added 1- benzyl benzimidazoles and toluene in three-necked flasks of the 100ml with return duct, under nitrogen protection slowly
The bromo- 1- propylene of 3- is added dropwise, proportionate relationship is 1g between the bromo- 1- propylene three of 1- benzyl benzimidazoles, toluene, 3- of addition:15-
20ml:1.5-1.7ml after being added dropwise, is warming up to 110 DEG C, continues heating stirring and reacts 72h.After reaction, system is cold
But after, solvent evaporated, product obtains white solid, as bromination 1- benzyls -3- allyl benzos through 20ml re-crystallizing in ethyl acetate
Imidazole salts.
Prepared material is applied to the separation and concentration of highly polar material, separation and the richness of polar compound can be improved
Collect efficiency, other than with hydrophobic and cationic exchange interaction mechanism, π-π effects, pi-electron transfer etc. is further related to, in complexity
There is potential application value in the separation analysis of sample.
Description of the drawings
The infrared spectrogram of Fig. 1 mercaptopropyltriethoxysilanes bonded silica gel (Sil-MPS).
The infrared spectrogram of Fig. 2 benzimidazole ionic liquid Solid Phase Extraction materials.
Tetra- kinds of alkylated purines compounds of Fig. 3（1 μg/mL）Separation chromatogram,
In figure：Peak 1, N3Methyl adenine；Peak 2, N7Methyl guanine；Peak 3, N3Ethyl adenine；Peak 4, N7Ethyl
Guanine.
Urine sample sample chromatogram figures of the Fig. 4 without Solid Phase Extraction.
Fig. 5 Solid Phase Extraction treated urine sample mark-on (0.05 μ g/ml) chromatogram
In figure：Peak 1, N3Methyl adenine；Peak 2, N7Methyl guanine；Peak 3, N3Ethyl adenine；Peak 4, N7Ethyl
Guanine.
Powdered milk sample chromatograms of the Fig. 6 without sample pre-treatments.
Powdered milk sample chromatograms of the Fig. 7 after Solid Phase Extraction.
Specific implementation mode
The present invention is with reference to embodiments（Attached drawing）It is described in further detail：
Preparation method embodiment
The specific preparation process of benzimidazole ionic liquid Solid Phase Extraction material is as follows：
（1）Prepare activated silica gel：
It is 480 m by 40-75 μm of grain size, specific surface area2The spherical porous silica gel 10g of/g immerses the salt of volumetric concentration 10%
In sour 100-120 ml, 6-8h is impregnated, the lower 14-16h that flows back is stirred, removes metal ion, filtered with G5 sand core funnels, with steaming again
Water is rinsed repeatedly to neutrality, is washed 2-3 times with methanol, acetone successively, and 6-8h is dried in vacuo at 120 DEG C, is obtained surface and is uniformly divided
The activated silica gel of cloth hydroxyl.
（2）The synthesis of bromination 1- benzyl -3- allyl benzene benzimidazole salts
1- benzyl benzimidazoles are added in three-necked flasks of the 100ml with return duct（2.1g, 0.01 mol）And 40ml
Toluene is slowly added dropwise the bromo- 1- propylene (3.4ml, 0.04mol) of 3- under nitrogen protection, after being added dropwise, is warming up to 110 DEG C, after
Continuous heating stirring reacts 72h.After reaction, after system being cooled down, solvent evaporated, product through 20ml re-crystallizing in ethyl acetate,
Obtain white solid 2.95g, yield 90%.Related assays data are as follows：Fusing point m.p. 206.3-206.4 DEG C.Nuclear magnetic resonance spectroscopy：
1H NMR（500MHz, CDCl3）δ 11.33（s, 1H）,7.75 (d, J=8.2Hz, 1H), 7.64 (d, J=8.2Hz,
1H),7.60 (t,J=7.7Hz,1H), 7.56 (d, J=8.3Hz, 2H), 7.54 (s, 1H), 7.33 (dt, J=
20.1, 6.4Hz, 3H), 6.15 (ddt, J=16.4, 10.2, 6.1Hz,1H), 5.47 (d, J=41.0Hz,2H),
5.33 (s,2H)。13C NMR（151MHz, CDCl3）δ 145.60, 135.63, 134.18, 132.48, 132.26,
132.07, 131.30, 130.13, 130.06, 124.81, 116.61, 54.39, 53.13.
（3）Prepare mercaptopropyltriethoxysilane SiClx glue：
3- mercaptopropyltriethoxysilanes 6ml is mixed with dry toluene 40ml, is added under 15-25r/m magnetic agitations
Activated silica gel 3g, and 110 DEG C are warming up to, it flows back under nitrogen protection for 24 hours；Then use G5 sand core funnels filter, successively use methanol,
Redistilled water, acetone are dried in vacuo 10-12h at washing 1-2 times, 50-60 DEG C, obtain mercaptopropyltriethoxysilane SiClx glue
（Sil-MPS）；
（4）The preparation of benzimidazole ionic liquid Solid Phase Extraction material
Preparation method is：By bromination 1- benzyl -3- allyl benzene benzimidazole salts（1.64g 5mmol）, to allyl benzene sulphur
Sour sodium（1.84g,10mmol）, 3.0g mercaptopropyltriethoxysilane SiClx glue be added in 80ml acetonitrile solvents, add and urge
Agent azodiisobutyronitrile 0.2g, under nitrogen protection, under the catalysis of catalyst 60 DEG C of reactions for 24 hours, filtering, use successively toluene,
Methanol, water and acetone respectively washed once, and 10-12h is dried in vacuo at 60 DEG C to get benzimidazole ionic liquid Solid Phase Extraction material
Material.
Above-mentioned material is characterized using infra-red sepectrometry, compares mercaptopropyltriethoxysilane bonded silica gel
(Sil-MPS) and the infrared spectrogram of benzimidazole ionic liquid Solid Phase Extraction material（Referring to Fig. 1 and 2）It can be seen that benzo
The infrared spectrogram of imidazole ion liquid Solid Phase Extraction material has had more 1483 cm-1, 1545 cm-1, 1596 cm-1Three peaks,
This is the characteristic peak of aromatic compound, illustrates that benzimidazole and benzene sulfonic acid group are successfully bonded to above silica gel.
The material of preparation is characterized using elemental microanalysis method, the results showed that the carbon of prepared Sil-MPS, hydrogen,
Sulfur content is 4.48%, 1.25% and 3.92%, and the carbon of the Solid Phase Extraction material of prepared benzimidazole ionic liquid,
Hydrogen, sulphur, nitrogen element content are 11.48%, 2.00%, 0.65% and 4.62%, and the 1- being bonded is calculated according to the variation of nitrogen content
Benzyl -3- allyl benzimidazoles are 0.87 μm of ol/m2, according to the variation calculation key of sulfur content close to allyl
The amount of benzene sulfonic acid sodium salt is 0.70 μm of ol/m2.The result shows that 1- benzyls -3- allyls benzimidazole and to allyl benzene sodium sulfonate
Successfully it has been bonded to above silica gel.Benzimidazole group and benzene sulfonic acid base are introduced in the Solid Phase Extraction material of synthesis
Group, making Solid Phase Extraction material not only has cationic exchange interaction, moreover it is possible to which there is π-π effects, pi-electron to shift, but also have
Certain hydrophily has multiple immixture pattern.
Application Example 1
Using prepared Solid Phase Extraction material, it has been investigated to the highly polar alkylation purine in urine sample
The enriching and purifying performance of substance.Concrete operation step is as follows：
1）The filling of solid-phase extraction column：
By commercially available polypropylene void column pipe（Specification is 500mg/6ml, the production of Di Ma Science and Technology Ltd.s）First use water and first
Alcohol cleans；Polypropylene sieve plate is inserted in column tube bottom, accurately weighs 500 mg（It is accurate to 0.1 mg）Solid phase prepared by the present invention
Extraction stuffing benzimidazole ionic liquid Solid Phase Extraction material；Appropriate jolt ramming, shake it is flat after, in filler upper end filling polypropylene sieve
Plate, appropriateness are compacted, and the solid phase extraction column filled is spare；
2）Solid phase extraction procedure and liquid-phase condition：
Influence the Solid Phase Extraction rate of recovery an important factor for include：Solid Phase Extraction material utilization amount, eluant, eluent type, eluant, eluent body
Product and loading speed etc..Experiment is using the rate of recovery of four kinds of alkylated purines class compounds as foundation, respectively to above-mentioned several shadows
The factor of sound is optimized, and obtains best Solid Phase Extraction treatment conditions.Process is as follows after optimization：
The solid phase extraction column filled is hanged into disposed upright on rack for test tube, with the activation of 3mL methanol, 3mL water balances, is then used
The processed samples of 5mL are added in pipette；After loading, eluted with the elution of 20% methanol of 3mL, 60% methanol of 3mL；Eluent is received
In collection to 10mL centrifuge tubes, it is concentrated into 0.5 ml, after crossing 0.22 mm filter membranes, is analyzed for HPLC.
High-efficient liquid phase chromatogram condition：Liquid-phase chromatographic column（Waters T3,3 μm, 4.6mm × 100mm）, mobile phase is first
- 0.1% formic acid aqueous ammonium of alcohol（20:80, v/v）, Detection wavelength is 230 nm, and flow velocity 0.4mL/min, column temperature is 30 DEG C.At this
Under liquid-phase condition, four kinds of polar alkylated purines substance separation chromatograms as shown in Figure 3, divide under this condition by four kinds of compounds
From good.Fig. 4 is the urine sample chromatogram handled without Solid Phase Extraction, and comparison diagram 3 and Fig. 4 can be seen that urine sample sample mesostroma
It is more complicated, detection can be interfered, influence the accuracy of result.Fig. 5 is the chromatogram of mark-on in urine sample sample, by figure
It can be seen that Solid Phase Extraction is after carrying out pre-treatment to sample, the matrix in urine sample sample is examined almost without interference through liquid chromatogram
It surveys, the rate of recovery of several substances shows that its rate of recovery is high, concentration effect is good 95% or so after Solid Phase Extraction.In addition to this, institute
The Solid Phase Extraction material of preparation can reuse after 5 ml methanol, 5ml water wash, therefore can be greatly cost-effective,
Reduce testing cost.
The experimental results showed that the Solid Phase Extraction column of material has good chromatographic performance, it can be in selective absorption urine sample
Alkylated purines class compound, effectively remove the interference impurity in urine sample sample, improve the specificity of analysis method, can be with
Separation, purifying and enrichment for highly polar substance in the samples such as urine sample.
Application Example 2
Solid Phase Extraction material isolates and purifies effect to melamine in dairy produce
Concrete operation step is as follows：
1）The filling of solid-phase extraction column：With Application Example 1
2）Solid phase extraction procedure and liquid-phase condition：
Chromatographic column：Waters Atlantis HILIC columns（150 mm × 2.1 mm, 5 μm）, -0.1% first of mobile phase acetonitrile
Sour aqueous ammonium（90:10, v/v）, 0.4 ml/min of flow velocity, sample size：5 μ L, Detection wavelength：240 nm, column temperature：20℃.
Experimental result：It weighs 2.00g samples and 15ml trichloroacetic acids and 5mL acetonitriles, ultrasonic vibration centrifugation extraction is added.It takes
Solid-phase extraction columns of the clear liquid 5ml after 3mL methanol, the activation of 3mL water, with 2ml methanol-waters（1:1）After elution, 5% ammonia of 5ml is used
Water beetle alcoholic solution elutes, and collects efflux, is dried up with nitrogen at 40 DEG C；- 0.1% formic acid aqueous ammonium of 1ml acetonitriles is added（90:
10, v/v）Dissolving, with 0.22 μm of organic membrane filtration, filtrate measures for HPLC.
From fig. 6 it can be seen that impurity content is larger in untreated powdered milk sample, the separating degree of object and impurity compared with
Difference, it is easily disturbed.After prepared Solid Phase Extraction material processing（Fig. 7）, sample impurity significantly reduces, melamine with it is miscellaneous
It is apparent to isolate and purify effect for the separating degree higher of matter.
Claims (6)
1. a kind of cation with immixture pattern exchanges Solid Phase Extraction material, it is characterised in that：Specifically a kind of benzo
Imidazole ion liquid Solid Phase Extraction material, structural formula I are：
。
2. a kind of cation as described in claim 1 with immixture pattern exchanges the preparation side of Solid Phase Extraction material
Method, it is characterised in that：It is to be reacted in toluene environment with 3- mercaptopropyltriethoxysilanes by the spherical porous silica gel after activating
Generate mercaptopropyltriethoxysilane SiClx glue, the mercaptopropyltriethoxysilane SiClx glue again with bromination 1- benzyl -3- allyls
Base benzoglioxaline salt is added in acetonitrile solvent allyl benzene sodium sulfonate jointly, adds catalyst azodiisobutyronitrile, nitrogen
It under gas shielded, is reacted, filters, respectively washed once with toluene, methanol, water and acetone successively, it is dry to make to get with mixing
Solid Phase Extraction material --- benzimidazole ionic liquid Solid Phase Extraction material is exchanged with the cation of pattern.
3. preparation method according to claim 2, it is characterised in that：Specific preparation process is as follows：
（1）Prepare activated silica gel：
Spherical porous silica gel is immersed in the hydrochloric acid of volumetric concentration 10%, impregnate 6-8h, stirred the lower 14-16h that flows back, remove metal
Ion is filtered with G5 sand core funnels, is rinsed with redistilled water to neutrality, washed 2-3 times with methanol, acetone successively repeatedly, at 120 DEG C
It is dried in vacuo 6-8h, obtains to surface and is uniformly distributed the activated silica gel of hydroxyl；
（2）Prepare mercaptopropyltriethoxysilane SiClx glue：
3- mercaptopropyltriethoxysilanes are mixed with dry toluene, activated silica gel is added under 15-25r/m magnetic agitations, adds
The proportionate relationship of the 3- mercaptopropyltriethoxysilanes, dry toluene and the activated silica gel three that enter are 1 ml:5-8 ml:0.3-
0.6 g, and 110 DEG C are warming up to, it flows back under nitrogen protection for 24 hours；Then it uses G5 sand core funnels to filter, is steamed successively with methanol, again
Water, acetone wash and are dried in vacuo 10-12h at each 1-2 times, 50-60 DEG C, obtain mercaptopropyltriethoxysilane SiClx glue；
（3）The preparation of benzimidazole ionic liquid Solid Phase Extraction material
Preparation method is：By bromination 1- benzyl -3- allyl benzenes benzimidazole salt, to allyl benzene sodium sulfonate, three ethoxy of mercapto propyl
Base silane SiClx glue is added in acetonitrile solvent, adds catalyst azodiisobutyronitrile, the bromination 1- benzyl -3- allyls of addition
Base benzoglioxaline salt, to the ratio of allyl benzene sodium sulfonate, mercaptopropyltriethoxysilane SiClx glue, acetonitrile and azodiisobutyronitrile
Example relationship is 1g: 1-1.3g: 1.7-2g: 45-50ml:0.1-0.15 g, under nitrogen protection, 60 under the catalysis of catalyst
DEG C reaction 24-26h, filtering, respectively washed once with toluene, methanol, water and acetone successively, 10-12h be dried in vacuo at 60 DEG C, i.e.,
Obtain benzimidazole ionic liquid Solid Phase Extraction material.
4. preparation method according to claim 2 or 3, it is characterised in that：The grain size 40-75 μ of the spherical porous silica gel
M, specific surface area is 480 m2/g。
5. preparation method according to claim 2 or 3, it is characterised in that：Bromination 1- benzyl -3- allyl benzene benzimidazole salts
Synthetic method it is as follows：
1- benzyl benzimidazoles and toluene are added in three-necked flasks of the 100ml with return duct, is slowly added dropwise under nitrogen protection
The bromo- 1- propylene of 3-, proportionate relationship is 1g between the bromo- 1- propylene three of 1- benzyl benzimidazoles, toluene, 3- of addition:15-
20ml:1.5-1.7ml after being added dropwise, is warming up to 110 DEG C, continues heating stirring and reacts 72h；After reaction, system is cold
But after, solvent evaporated, product obtains white solid, as bromination 1- benzyls -3- allyl benzos through 20ml re-crystallizing in ethyl acetate
Imidazole salts.
6. it is rich in separation that a kind of cation with immixture pattern as described in claim 1 exchanges Solid Phase Extraction material
Collect the application in highly polar compound.
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