CN104130358A - Preparation method for morin molecularly imprinted silica gel - Google Patents
Preparation method for morin molecularly imprinted silica gel Download PDFInfo
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- CN104130358A CN104130358A CN201410251229.2A CN201410251229A CN104130358A CN 104130358 A CN104130358 A CN 104130358A CN 201410251229 A CN201410251229 A CN 201410251229A CN 104130358 A CN104130358 A CN 104130358A
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Abstract
The invention discloses a preparation method for a morin molecularly imprinted silica gel. A morin molecule is adopted as the template, acrylamide or methacrylic acid is taken as the functional monomer, and silica gel surface grafting imprinting technology is employed to synthesize morin molecularly imprinted silica gel. The preparation method includes three steps: (1) preparation of N-propyl maleamic acid modified silica gel; (2) synthesis of a morin molecularly imprinted silica gel primary product; and (3) purification treatment of morin molecularly imprinted silica gel. The morin molecularly imprinted silica gel prepared by the method has high adsorption capacity and good selective adsorption properties. Experiments validate and summarize that morin imprinted silica gel has a good recovery rate on actual samples, and therefore has good application prospects in molecular recognition, enrichment, separation, detection and other aspects.
Description
technical field:
The present invention relates to the preparation method of the molecular imprinting silica gel of a kind of simple and fast enrichment, separation and detection morin monomer.
background technology:
Morin is a kind of light yellow pigment extracting from the bark of moraceae plants and some herbal medicine, has antioxygenation, can be used for gum health care (
[1]rB Cameron, the sub-nurse of R Su Xi Raman, H Trivedi, C irrigates Lei Er. the oral cavity composition that comprises morin: Britain. CN200680039583.2. [P]. 2008-10-29), morin is also indispensable a kind of developer in chemical analysis simultaneously.The preparation method of morin molecular imprinting silica gel all rarely has report with it for extracting the method for purifying at present.Molecular imprinting be preparation to template molecule have that specificity is selected and high stability molecular template technology (
[2]wang Changlu, Gu Qimei, Li Fengjuan, Wang Yurong, Chen Mianhua. the preparation method of fats molecularly imprinted polymer: China. CN109106186 A. [P] 2010-12-08).It is function monomer that acrylamide or methacrylic acid are take in the present invention, utilize Silica Surface grafting engram technology to synthesize morin molecular imprinting silica gel, and this imprinted silica gel has good adsorption selectivity.Therefore at aspects such as the identification enrichment of molecule, separation and detections, demonstrated good application prospect.
summary of the invention:
Technical scheme of the present invention is to take morin molecule as template, acrylamide or methacrylic acid are function monomer, utilize Silica Surface grafting engram technology to synthesize morin molecular imprinting silica gel, for selective enrichment and the rapid detection of morin in complex sample provides new approach.
the present invention includes following steps:
The preparation of 1.N-propyl group maleinamic acid modified silica-gel:
1. silica gel reflux in concentrated acid is made to filter after Silica Surface activation, with second distillation, be washed to neutrality, dry standbyly after activated silica gel.
2. get silica gel prepared by 10g aforesaid method and be dissolved in 250ml round-bottomed flask with 100mL toluene, under vigorous stirring, dropwise adding 10mL silane coupling agent (APTES), stirring and refluxing 6h.Product is filtered, and with toluene, ethanol and ether washing, under 60 ℃ of conditions, dry 3h obtains the silica gel of grafting amino successively.
3. in above-mentioned amination silica gel, add 100mL 0.5molL
-1the dimethyl formamide solution of maleic anhydride, under room temperature, stir and make it to react 24h, after filtration, successively with dimethyl formamide, ethanol, ether washing, room temperature vacuum-drying makes N-propyl group maleinamic acid modified silica-gel.
2. morin molecular imprinting silica gel head product is synthetic:
Take in the tetrahydrofuran solution that 0.2g morin is dissolved in 40mL, the silica gel that adds wherein 2gN-propyl group maleinamide to modify, stirring reaction 0.5h, add 0.1522g acrylamide (or 0.3444g methacrylic acid) stirring reaction 0.5h, the initiator Diisopropyl azodicarboxylate that adds successively again 1.192g pentaerythritol triacrylate and 40mg, stirring reaction 12h under logical nitrogen and 60 ℃ of conditions, obtains the head product of morin molecular imprinting silica gel.
3. the purification process of morin molecular imprinting silica gel:
Prepared morin molecular imprinting silica gel head product is carried out filtration treatment and with the methyl alcohol/acetic acid solution washing of 8:2 (V:V), removes template molecule and unreacted compound, then with methyl alcohol, be washed till neutrality and (remove H excessive in system
+), then filter, be dried to obtain end product morin molecular imprinting silica gel.
Step 1. in, the particle diameter of described silica gel is 50～200 orders, described acid can be hydrochloric acid, sulfuric acid or nitric acid etc., the volumetric molar concentration of described acid solution is 8～10molL
-1, silica gel and sour consumption are that every gram of silica gel adds 5～10ml acid, the time of described immersion is 0.5～10h, and described water ultrapure water, the temperature of described oven dry is 40～120 ℃.
Above-mentioned concrete reaction process as shown in Figure 1.
the present invention has the following advantages:
Preparation process is easy, easy to operate, prepared morin molecular imprinting silica gel has higher loading capacity and certain selective adsorption function to morin molecule, the morin molecular imprinting silica gel of synthesized can be packed into selective extraction, enrichment, the separation and detection that solid phase extraction column is applied to morin molecule in solution.
accompanying drawing explanation:
The process schematic diagram of imprinted silica gel polymerization in Fig. 1 the present invention.
The impact of different concussion time on non-imprinted silica gel absorption morin in Fig. 2 the present invention.
Fig. 3 is respectively morin molecule and the morin schematic arrangement the present invention relates to.
embodiment:
Below by embodiment, the present invention is further illustrated.
Embodiment 1:
The activation of silica gel: be that 50 order silica gel 5.0g silica gel are in 25mL 8molL by particle diameter
-1in concentrated hydrochloric acid, reflux 4h, with the surface of activated silica gel, is washed to pH value with second distillation after filtration and is neutral, standby after under 80 ℃ of conditions, dry 12h obtains activated silica gel.
The preparation of morin molecular imprinting silica gel: get silica gel prepared by 20g aforesaid method and be dissolved in 500ml round-bottomed flask with 200mL toluene, under vigorous stirring, slowly add 20mL silane coupling agent (3-aminopropyl-triethoxyl silane), reflux 6h under agitation condition.Product is filtered, and with toluene, ethanol and ether washing, under 60 ℃ of conditions, dry 3h obtains the silica gel of grafting amino successively.In above-mentioned ammonification silica gel, add 200mL 0.5molL
-1the dimethyl formamide solution of maleic anhydride, stirring reaction 24h under room temperature, after filtration, successively with dimethyl formamide, ethanol, ether washing, room temperature vacuum-drying makes N-propyl group maleinamic acid modified silica-gel.Take in the tetrahydrofuran solution that 0.4g morin is dissolved in 80mL, add wherein 4gN-propyl group maleinamic acid modified silica-gel stirring reaction 0.5h, add 0.3044g acrylamide (or 0.6888g methacrylic acid) stirring reaction 0.5h, add successively again 2.384g pentaerythritol triacrylate and 80mg initiator Diisopropyl azodicarboxylate, stirring reaction 12h under logical nitrogen and 60 ℃ of conditions.Prepared morin molecular imprinting silica gel head product is carried out to filtration treatment wash to remove template molecule and unreacted compound with methyl alcohol/acetic acid solution of 8:2 (V:V), then with methyl alcohol, be washed till neutrality and (remove excessive H
+), then filter, the dry morin molecular imprinting silica gel product that finally obtains.
Embodiment 2:
Take a series ofly by each 1g of the morin imprinted silica gel of embodiment 1 synthesized (take acrylamide as function monomer), add respectively 100mL 1.0mmolL
-1morin solution, at 25 ℃ with 200rmin
-1vibration, investigates the impact on the absorption of morin of morin molecular imprinting silica gel under different duration of oscillations, and in solution, the measuring method of morin is transferred in 10mL colorimetric cylinder for getting the plain adsorption liquid of appropriate canopy skin, adds 0.2mL 2 * 10
-2moll
-1alC1
3solution, is diluted to scale with dehydrated alcohol, and standing 15min selects 1cm cuvette to be detected on the fluorescence intensity at excitation wavelength 365nm and emission wavelength 498nm place, does blank assay simultaneously.According to the change calculations in conjunction with concentration of substrate in the solution of front and back, go out imprinted silica gel the binding capacity of substrate morin is adsorbed to the impact of morin to investigate different duration of oscillations on imprinted silica gel, its result as shown in Figure 2.
Embodiment 3:
Morin molecular imprinting silica gel and non-imprinted silica gel adsorb embodiment to different substrate selectives:
Selecting morin molecule and the Nobiletin very similar to morin molecular structure is substrate, and their molecular structure is respectively as shown in the A of Fig. 3 and B.
Take tetrahydrofuran (THF) as solvent, studied morin imprinted silica gel and the non-imprinted silica gel selective binding characteristic to substrate, balance combined techniques has been measured morin imprinted silica gel and the binding capacity of non-imprinted silica gel to substrate, and its result is as shown in table 1.
Table 1
Binding capacity (the μ molg of different substrates on morin imprinted silica gel and non-imprinted silica gel
-1)
The effect of many document announcement imprinted silica gels and microsphere is interactional synergy between space size and shape, functional group, relevant with space structure.From table 1, imprinted silica gel is obviously greater than the binding capacity of non-imprinted silica gel to morin to the binding capacity of morin, is due to the 3 D stereo configuration that imprinted silica gel forms, to be suitable for the space structure of morin; Imprinted silica gel to the binding capacity of morin than imprinted silica gel to large many of the binding capacity of Nobiletin, showing imprinted silica gel has good selectivity to morin.
Embodiment 4:
Take a series of each 100mg of morin imprinted silica gel by embodiment 1 synthesized and pack into and in Solid-Phase Extraction blank pipe, make solid phase extraction column to investigate the rate of recovery of synthesized morin imprinted silica gel to mark-on morin in tetrahydrofuran (THF), wherein not adding timestamp sample tetrahydrofuran (THF) used is 1.0L; Adding scalar is 2 μ molL
-1time, volume of sample used is 1.0L; Adding scalar is 4.0 μ molL
-1time, sample used is volume 1.0L.Loading flow velocity 4.0mLmin in experiment
-1, by 3.0mL concentration, be 1.0molL
-1hydrochloric acid carries out wash-out, and elution flow rate is 1.2mLmin
-1.In solution, hesperetin content is used fluorescent spectrophotometer assay, and morin imprinted silica gel is as shown in table 2 to the specimen sample rate of recovery.
Table 2
From implementing can to find out that morin imprinted silica gel is higher to the rate of recovery of actual sample 4, up to 100%.
Claims (3)
1. the preparation method of morin molecular imprinting silica gel, its feature comprises the following steps successively:
1. the preparation of N-propyl group maleinamic acid modified silica-gel:
Silica gel reflux in concentrated acid is made to filter after Silica Surface activation; extremely neutral with second distillation washing washing; dry standbyly after activated silica gel; get silica gel prepared by 10g aforesaid method and be dissolved in 250ml round-bottomed flask with 100mL toluene; under vigorous stirring, dropwise add 10mL silane coupling agent 3-aminopropyl-triethoxyl silane, stirring and refluxing 6h;
Product is filtered, and with toluene, ethanol and ether washing, under 60 ℃ of conditions, dry 3h obtains the silica gel of grafting amino, in above-mentioned amination silica gel, adds 100mL 0.5molL successively
-1the dimethyl formamide solution of maleic anhydride, under room temperature, stir and make it to react 24h, after filtration, successively with dimethyl formamide, ethanol, ether washing, room temperature vacuum-drying makes N-propyl group maleinamic acid modified silica-gel;
2. morin molecular imprinting silica gel head product is synthetic:
Take in the tetrahydrofuran solution that 0.2g morin is dissolved in 40mL, add wherein 2gN-propyl group maleinamic acid modified silica-gel, stirring reaction 0.5h, add 0.1522g acrylamide (or 0.3444g methacrylic acid) stirring reaction 0.5h, the initiator Diisopropyl azodicarboxylate that adds successively again 1.192g pentaerythritol triacrylate and 40mg, stirring reaction 12h under logical nitrogen and 60 ℃ of conditions, obtains morin molecular imprinting silica gel head product;
3. the purification process of morin molecular imprinting silica gel:
Prepared morin molecular imprinting silica gel head product is carried out filtration treatment and with the methyl alcohol/acetic acid solution washing of 8:2 (V:V), removes template molecule and unreacted compound, then with methyl alcohol, be washed till neutrality and (remove H excessive in system
+), then filter, be dried to obtain end product morin molecular imprinting silica gel.
Step as claimed in claim 1 1. in, the particle diameter that it is characterized in that described silica gel is 50～200 orders, described acid can be hydrochloric acid, sulfuric acid or nitric acid etc., the volumetric molar concentration of described acid solution is 8～10mol/L, silica gel and sour consumption are that every gram of silica gel adds 5～10ml acid, the time of described immersion is 0.5～10h, described water ultrapure water, and the temperature of described oven dry is 40～120 ℃.
3. the preparation method of morin molecular imprinting silica gel as claimed in claim 1 is characterized in that: morin molecule is template, and function monomer is acrylamide or methacrylic acid, and linking agent is pentaerythritol triacrylate, and initiator is Diisopropyl azodicarboxylate.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104744647A (en) * | 2014-12-09 | 2015-07-01 | 西南石油大学 | Preparation method of modified nano SiO2 graft copolymer |
| CN105044254A (en) * | 2015-06-23 | 2015-11-11 | 深圳中检联检测有限公司 | Method for preparing nitrofuran molecularly imprinted polymer microspheres |
| CN105085837A (en) * | 2014-12-09 | 2015-11-25 | 西南石油大学 | Modified nanometer SiO2-AA-AM copolymer |
-
2014
- 2014-06-06 CN CN201410251229.2A patent/CN104130358A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104744647A (en) * | 2014-12-09 | 2015-07-01 | 西南石油大学 | Preparation method of modified nano SiO2 graft copolymer |
| CN105085837A (en) * | 2014-12-09 | 2015-11-25 | 西南石油大学 | Modified nanometer SiO2-AA-AM copolymer |
| CN104744647B (en) * | 2014-12-09 | 2017-09-19 | 西南石油大学 | Modified Nano SiO2The preparation method of graft copolymer |
| CN105044254A (en) * | 2015-06-23 | 2015-11-11 | 深圳中检联检测有限公司 | Method for preparing nitrofuran molecularly imprinted polymer microspheres |
| CN105044254B (en) * | 2015-06-23 | 2018-02-09 | 深圳中检联检测有限公司 | The preparation method and application of itrofurans molecular blotting polymer microsphere |
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