CN103232572A - Molecular imprinting polymer for roxarsone detection, and preparation method thereof - Google Patents
Molecular imprinting polymer for roxarsone detection, and preparation method thereof Download PDFInfo
- Publication number
- CN103232572A CN103232572A CN2013101300827A CN201310130082A CN103232572A CN 103232572 A CN103232572 A CN 103232572A CN 2013101300827 A CN2013101300827 A CN 2013101300827A CN 201310130082 A CN201310130082 A CN 201310130082A CN 103232572 A CN103232572 A CN 103232572A
- Authority
- CN
- China
- Prior art keywords
- preparation
- template
- luo kesha
- molecularly imprinted
- arsine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The invention belongs to the technical field of material chemistry, and discloses a molecular imprinting polymer for roxarsone detection, and a preparation method thereof. The molecular imprinting polymer preparation method comprises the following steps: carrying out polymerization of a template, a pore forming agent, a functional monomer, a cross-linking agent and an initiator for 8-48 h at a temperature of 50-80 DEG C, and removing the template to obtain the molecular imprinting polymer for roxarsone detection. According to the present invention, a roxarsone recovery rate of the prepared molecular imprinting polymer is more than 90%, and the prepared molecular imprinting polymer shows a high roxarsone cross reaction, has high selectivity and high specificity, and provides broad application prospects in the field of application of the prepared molecular imprinting polymer as a sample purification pretreatment material for roxarsone analysis in feeds, animal tissues, environment water and other matrixes.
Description
Technical field
The invention belongs to material chemistry technical field, particularly a kind of molecularly imprinted polymer for detection of the Luo Kesha arsine and preparation method thereof.
Background technology
Luo Kesha arsine (Roxarsone), chemistry is by name: 3-nitro-4-hydroxyl-phenylarsonic acid, with Pro-gen 90 (P-Arsanilic acid) be for many years in countries in the world widely used two kinds contain the arsenic feed and add medicine, and the Luo Kesha arsine is used wider than Pro-gen 90.The Luo Kesha arsine is most economical a kind of multi-functional organic arsine preparation, has the promotion growth of animals or poultry, improves food conversion ratio, and promotes the poultry pigment deposition, can increase the effect of other anticoccidial drug to poultry; Dysentery and the enteritis for the treatment of pig improve laying rate of laying hen.The use that China Ministry of Agriculture ratified this medicine in 1996 has domesticly afterwards begun mass production gradually, and is widely used in poultry husbandry and pig industry.But discovered afterwards that it caused environmental pollution easily, European Union in 1999 has prohibited and has used the Luo Kesha arsine as chicken feed interpolation medicine.Consider that animal food safety, China Ministry of Agriculture announce the maximum residue limit(MRL) of also having formulated roxarsone for No. 235.This medical instrument has certain residual toxicity, to the mankind have potential carinogenicity may, therefore its detection is also become the focus of domestic and international research rapidly.But the pre-treating process that existing all Luo Kesha arsines detect all is the traditional solid phase extraction column (as MAX) of employing to be purified, and lacks selectivity, and specificity is not strong, thereby influences the sensitivity of whole detection method and accurately quantitative.
Molecular engram solid phase extraction technology based on similar Ag-Ab effect has highly selective and specificity, is a kind of Solid-Phase Extraction material with wide application prospect.If can be as antibody, the polymer adsorbing material that the Luo Kesha arsine is had highly selective of synthetic some similar antibody can improve sensitivity and accuracy that the Luo Kesha arsine detects greatly.
Molecular imprinting (molecular imprinting) is a new research field that develops rapidly based on molecular recognition theory in recent years, and molecular imprinting is also referred to as the technology of manufacturing " plastics antibody ".(molecular imprinting polymers is that a class inside has the hole of fixed size and shape and has the cross-linked high polymer of definite arranging functional group MIP) to molecularly imprinted polymer.Because MIP is customized according to microsphere, so it has specific molecule structure and functional group, can optionally identify microsphere.
The preparation of molecularly imprinted polymer generally will be by following three steps:
(1) function monomer accumulates in template molecule and forms reversible mixture on every side by interacting on (covalently or non-covalently key) with template molecule;
(2) copolymerization generation superpolymer takes place in function monomer and excessive linking agent in the presence of pore-creating agent;
(3) template molecule is dissociated out from superpolymer, in polymkeric substance, just formed can the recognition template molecule binding site.
This imprinted polymer can be used as the sensing member of stationary phase, catalysts selective, chemical sensor of liquid chromatography and Solid-Phase Extraction material etc., also is widely used in the clinical medicine analysis.
Summary of the invention
In order to overcome the deficiencies in the prior art, primary and foremost purpose of the present invention provides a kind of preparation method of the molecularly imprinted polymer for detection of the Luo Kesha arsine.This preparation method is with low cost, and is simple to operate.
Another object of the present invention provides the molecularly imprinted polymer for detection of the Luo Kesha arsine for preparing by above-mentioned preparation method.This molecularly imprinted polymer has highly selective and affinity to the Luo Kesha arsine, is more than 90% to the rate of recovery of Luo Kesha arsine.
The objective of the invention is to be achieved through the following technical solutions:
A kind of preparation method of the molecularly imprinted polymer for detection of the Luo Kesha arsine, may further comprise the steps: with template, pore-creating agent, function monomer, linking agent and initiator at 50～80 ℃ of polymerization 8～48 h, after removing template, namely get for the molecularly imprinted polymer that detects the Luo Kesha arsine;
Described template is Pro-gen 90 or ethyl p-hydroxybenzoate.
The ratio of described template, function monomer, linking agent, pore-creating agent and initiator is 1:2～16:10～40 ﹕, 1～200:10～60, and described ratio is mmol:mmol:mmol:mL:mg.
Described function monomer is 2-vinyl pyridine, methacrylic acid, vinylformic acid, 4-vinylpridine, to Ethenylbenzene formic acid or acrylamide.
Described linking agent is ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate or divinylbenzene;
Described pore-creating agent is more than one in methyl alcohol, acetonitrile, chloroform, the acetone; Preferred pore-creating agent is that simple acetonitrile or volume ratio is the methyl alcohol of 1:1 and the mixed solution of acetonitrile.Pore-creating agent will guarantee the abundant dissolving of template on the one hand, the pore-creating agent consumption has material impact to molecularly imprinted polymer intensity, the surface property of preparation on the other hand, pore-creating agent is also very crucial to the identification of imprinted polymer Luo Kesha arsine in the working medium system simultaneously, when pore-creating agent is selected methyl alcohol-acetonitrile (1:1, V/V) time, can prepare the molecularly imprinted polymer that the Luo Kesha arsine is had high degree of specificity identification.
Described initiator is water soluble starter or oil-soluble initiator; Described oil-soluble initiator is Diisopropyl azodicarboxylate; Described water soluble starter is ammonium persulphate.
A kind of preparation method of the molecularly imprinted polymer for detection of the Luo Kesha arsine, its preferred concrete steps are:
(1) preparation of prepolymer: add pore-creating agent in template, vortex to template is dissolved, and adds function monomer, and is ultrasonic, leaves standstill, and obtains prepolymer;
(2) polymerizing curable: in prepolymer, add linking agent and initiator, ultrasonic, logical nitrogen under the ice bath, sealing, polymerization in the vacuum drying oven obtains bulk polymer;
(3) for detection of the preparation of the molecularly imprinted polymer of Luo Kesha arsine: bulk polymer is treated to fine particle, and template is gone in the solvent orange 2 A washing, and after the solvent B washing, vacuum-drying namely gets for the molecularly imprinted polymer that detects the Luo Kesha arsine.
Ultrasonic time described in the step (1) is 5min; Time of repose is 1h;
Ultrasonic time described in the step (2) is 5min; The logical nitrogen time of described ice bath is 5min; The temperature of polymerization is 50～80 ℃ in the described vacuum drying oven, and the time is 8～48h.
Solvent orange 2 A described in the step (3) is the mixing solutions of acetic acid and methyl alcohol, and the volume ratio of acetic acid and methyl alcohol is 1:9 in the mixing solutions; The flow velocity of described solvent orange 2 A washing is below the 1mL/min; Described solvent B is methyl alcohol, and volume is 40mL; Described vacuum drying temperature is 60 ℃, and the time is 12h.
According to the molecularly imprinted polymer for detection of the Luo Kesha arsine that preparation method described above prepares, this molecularly imprinted polymer is more than 90% to the rate of recovery of Luo Kesha arsine.
Molecularly imprinted polymer of the present invention, find after testing: this polymkeric substance is used for Solid-Phase Extraction purifies (50mg/ post), polymkeric substance is about 930 μ g/g polymkeric substance in conjunction with the adsorptive capacity of Luo Kesha arsine; In the aqueous solution (tap water, underground and surface water), add Luo Kesha arsine recovery test and show that in 1.0～50 μ g/mL concentration were added horizontal extent, the Luo Kesha arsine rate of recovery was greater than 90%; The solid phase extraction column of molecularly imprinted polymer of the present invention filling, reuse 10 times after, the rate of recovery of Luo Kesha arsine is still greater than 80%.
The present invention has following advantage and effect with respect to prior art:
When (1) the present invention prepared molecularly imprinted polymer, the pore-creating agent of employing was that (1:1 V/V), is conducive to the dissolving of template to methyl alcohol-acetonitrile, makes the imprinted polymer specific recognition capability of preparation strong.
(2) preparation method of the present invention can be directly adds linking agent and initiator in the prepolymer and carries out 50～80 ℃ of thermopolymerizations then and solidify, can also carry out earlier carrying out 50～80 ℃ of thermopolymerizations curing again after the low temperature photopolymerization, can further improve the specificity of molecularly imprinted polymer like this.
(3) molecularly imprinted polymer of the present invention presents high affinity and selectivity to the Luo Kesha arsine in methyl alcohol and acetonitrile, and the rate of recovery is greater than 90%.
(4) the present invention is that the Luo Kesha arsine of MIP that template makes shows high cross reaction with ethyl p-hydroxybenzoate or Pro-gen 90, have high selectivity and specificity, with this is compared as the synthetic MIP of template with the Luo Kesha arsine, can prevent that Yin Luokesha arsine wash-out is incomplete, because " template leakage " among the MIP (residual Luo Kesha arsine template) causes the influence to Luo Kesha arsine detected result, have a wide range of applications as the sample purification pre-treatment material of analyzing Luo Kesha arsine in the matrix such as feed, animal tissues and ambient water during use.
Description of drawings
Fig. 1: Luo Kesha arsine acetonitrile solution is crossed the color atlas (10 μ g/mL) of MIP1 and NIP1 solid-phase extraction column;
Wherein, a: Luo Kesha arsine acetonitrile solution is crossed the color atlas of MIP1 Solid-Phase Extraction; B: Luo Kesha arsine acetonitrile solution is crossed the color atlas of NIP1 Solid-Phase Extraction.
Fig. 2: Luo Kesha arsine acetonitrile solution is crossed the color atlas (10 μ g/mL) of MIP2 and NIP2 solid-phase extraction column;
Wherein, c: Luo Kesha arsine acetonitrile solution is crossed the color atlas of MIP2 Solid-Phase Extraction; D: Luo Kesha arsine acetonitrile solution is crossed the color atlas of NIP2 Solid-Phase Extraction.
Fig. 3: Luo Kesha arsine polymer solution in water is crossed the color atlas (5 μ g/mL) of MIP1 and NIP1 solid-phase extraction column;
Wherein, e: Luo Kesha arsine polymer solution in water is crossed the color atlas of MIP1 solid-phase extraction column; F: Luo Kesha arsine polymer solution in water is crossed the color atlas of NIP1 solid-phase extraction column.
Fig. 4: Luo Kesha arsine surface water solution is crossed the color atlas of MIP2 and NIP2 solid-phase extraction column; (0.5 μ g/mL);
Wherein, g: Luo Kesha arsine surface water solution is crossed the color atlas of MIP1 solid-phase extraction column; H: Luo Kesha arsine surface water solution is crossed the color atlas of NIP1 solid-phase extraction column.
Fig. 5: Luo Kesha arsine underground water solution is crossed the color atlas of MIP2 and NIP2 solid-phase extraction column; (50 μ g/mL);
Wherein, i: Luo Kesha arsine underground water solution is crossed the color atlas of MIP2 solid-phase extraction column; J: Luo Kesha arsine underground water solution is crossed the color atlas of NIP2 solid-phase extraction column.
Fig. 6: the typical curve of the color atlas of Luo Kesha arsine.
Fig. 7: the sorption isotherm under 25 ℃ of the Luo Kesha arsines.
Embodiment
The present invention is described in further detail below in conjunction with embodiment and accompanying drawing, but embodiments of the present invention are not limited thereto.
(1) taking by weighing 0.166g(1mmoL) ethyl p-hydroxybenzoate is in test tube, adding 1mL acetonitrile after the vortex dissolving, adds 0.434mL(4mmoL again) 2-vinylpyridine function monomer, ultrasonic 5min leaves standstill 1h, forms prepolymer.
(2) in above-mentioned prepolymer, add ethylene glycol dimethacrylate 4mL(20mmoL) and Diisopropyl azodicarboxylate 60mg (0.365mmol), ultrasonic 5min, logical nitrogen 5min under the ice bath, sealing, polymerization 24h in 60 ℃ of vacuum drying ovens obtains bulk polymer.
(3) above-mentioned bulk polymer ground, cross 200 mesh sieves, with methyl alcohol repeatedly sedimentation remove fine particle, pack in the 15mL solid-phase extraction column, remove the template ethyl p-hydroxybenzoate with acetic acid and methanol mixed solution (volume ratio of acetic acid and methyl alcohol is 1:9) 200mL washing earlier, flow rate control is below 1mL/min, remove acetic acid with the 40mL methanol wash again, put dry 12 h in 60 ℃ of vacuum drying ovens, obtain the molecularly imprinted polymer for detection of the Luo Kesha arsine, put in the moisture eliminator preserve standby.The molecularly imprinted polymer for detection of the Luo Kesha arsine for preparing (MIP1) is compared with synthetic bulk polymer, and average yield reaches 64.5%.
The preparation of non-imprinted polymer (NIP1) is except adding the template molecule, all prepares as stated above and handles.
(1) taking by weighing 0.217g(1mmoL) Pro-gen 90 is in test tube, and adding 6mL methyl alcohol-acetonitrile solution (volume ratio of methyl alcohol and acetonitrile is 1:1) is after the vortex dissolving, add 0.434mL(4mmoL) 2-vinylpyridine function monomer, ultrasonic 5min leaves standstill 1h, forms prepolymer.
(2) in above-mentioned prepolymer, add ethylene glycol dimethacrylate 4mL(20mmoL) and Diisopropyl azodicarboxylate 60mg (0.365mmol), ultrasonic 5min, logical nitrogen 5min under the ice bath, sealing, polymerization 24h in 60 ℃ of vacuum drying ovens obtains bulk polymer.
(3) above-mentioned bulk polymer ground, cross 200 mesh sieves, with methyl alcohol repeatedly sedimentation remove fine particle, pack in the 15mL solid-phase extraction column, remove the template Pro-gen 90 with acetic acid and methanol mixed solution (volume ratio of acetic acid and methyl alcohol is 1:9) 200mL washing earlier, flow rate control is removed acetic acid with the 40mL methanol wash again below 1mL/min, put dry 12 h in 60 ℃ of vacuum drying ovens, obtain the molecularly imprinted polymer for detection of the Luo Kesha arsine, put in the moisture eliminator preserve standby.The molecularly imprinted polymer for detection of the Luo Kesha arsine for preparing (MIP2) is compared with synthetic bulk polymer, and average yield reaches 58.2%.
The preparation of non-imprinted polymer (NIP2) is except adding the template molecule, all prepares as stated above and handles.
Embodiment 3
(1) take by weighing 0.217g(1mmoL) Pro-gen 90 in test tube, add 6mL methyl alcohol-acetonitrile (1:1, V/V) solution after the vortex dissolving, add 0.171mL(2mmoL) methacrylic acid function monomer, ultrasonic 5min leaves standstill 1h, forms prepolymer.
(2) in above-mentioned prepolymer, add trimethylolpropane trimethacrylate 3.19mL(10mmoL) and Diisopropyl azodicarboxylate 10mg(0.06mmoL), ultrasonic 5min, logical nitrogen 5min under the ice bath, sealing, polymerization 48h in 50 ℃ of vacuum drying ovens obtains bulk polymer.
(3) above-mentioned bulk polymer ground, cross 200 mesh sieves, with methyl alcohol repeatedly sedimentation remove fine particle, pack in the 15 mL solid-phase extraction columns, first usefulness acetic acid and methanol mixed solution (1:9, V/V) the template Pro-gen 90 is removed in the 200mL washing, and flow rate control is below 1mL/min, remove acetic acid with the 40mL methanol wash again, put dry 12h in 60 ℃ of vacuum drying ovens, obtain the molecularly imprinted polymer for detection of the Luo Kesha arsine, put in the moisture eliminator preserve standby.The molecularly imprinted polymer for detection of the Luo Kesha arsine for preparing is compared with synthetic bulk polymer, and average yield reaches 52.6%.
(1) taking by weighing 0.166g(1mmoL) ethyl p-hydroxybenzoate is in test tube, adding 10.5mL acetonitrile after the vortex dissolving, adds 1.82mL(16mmoL again) to Ethenylbenzene formic acid function monomer, ultrasonic 5min leaves standstill 1h, forms prepolymer.
(2) in above-mentioned prepolymer, add divinylbenzene 5.60mL(40mmoL) and Diisopropyl azodicarboxylate 60mg(0.365mmoL), ultrasonic 5min, logical nitrogen 5min under the ice bath, sealing, polymerization 48h in 50 ℃ of vacuum drying ovens obtains bulk polymer.
(3) above-mentioned bulk polymer ground, cross 200 mesh sieves, with methyl alcohol repeatedly sedimentation remove fine particle, pack in the 15mL solid-phase extraction column, remove the template ethyl p-hydroxybenzoate with acetic acid and methanol mixed solution (volume ratio of acetic acid and methyl alcohol is 1:9) 200mL washing earlier, flow rate control is removed acetic acid with the 40mL methanol wash again below 1mL/min, put dry 8h in 80 ℃ of vacuum drying ovens, obtain the molecularly imprinted polymer for detection of the Luo Kesha arsine, put in the moisture eliminator preserve standby.The molecularly imprinted polymer for detection of the Luo Kesha arsine for preparing is compared with synthetic bulk polymer, and average yield reaches 48.3%.
(1) take by weighing 0.217 g(1 mmoL) Pro-gen 90 in test tube, add 9.3 mL methyl alcohol-acetonitrile (1:1, V/V) solution, after the vortex dissolving, add 1.42 mL(16 mmoL) the methacrylic acid function monomer, ultrasonic 5 min, leave standstill 1 h, form prepolymer.
(2) in above-mentioned prepolymer, add trimethylolpropane trimethacrylate 12.8 mL(40mmoL) and Diisopropyl azodicarboxylate 60mg(0.365mmoL), ultrasonic 5 min, logical nitrogen 5 min under the ice bath, sealing, polymerization 48 h obtain bulk polymer in 50 ℃ of vacuum drying ovens.
(3) above-mentioned bulk polymer ground, cross 200 mesh sieves, with methyl alcohol repeatedly sedimentation remove fine particle, pack in the 15 mL solid-phase extraction columns, first usefulness acetic acid and methanol mixed solution (1:9, V/V) the template Pro-gen 90 is removed in 200 mL washing, and flow rate control is below 1 mL/min, remove acetic acid with 40 mL methanol wash again, put dry 12 h in 60 ℃ of vacuum drying ovens, obtain the molecularly imprinted polymer for detection of the Luo Kesha arsine, put in the moisture eliminator preserve standby.The molecularly imprinted polymer for detection of the Luo Kesha arsine for preparing is compared with synthetic bulk polymer, and average yield reaches 46.7%
Embodiment 6
(1) taking by weighing 0.166g(1 mmoL) ethyl p-hydroxybenzoate is in test tube, adding 3mL acetonitrile after the vortex dissolving, adds 0.23 mL(2mmoL again) to Ethenylbenzene formic acid function monomer, ultrasonic 5 min leave standstill 1 h, form prepolymer.
(2) in above-mentioned prepolymer, add divinylbenzene 1.4mL(10mmoL) and Diisopropyl azodicarboxylate 10mg(0.06 mmoL), ultrasonic 5 min, logical nitrogen 5 min under the ice bath, sealing, polymerization 48 h obtain bulk polymer in 50 ℃ of vacuum drying ovens.
(3) above-mentioned bulk polymer ground, cross 200 mesh sieves, with methyl alcohol repeatedly sedimentation remove fine particle, pack in the 15 mL solid-phase extraction columns, remove the template ethyl p-hydroxybenzoate with acetic acid and methanol mixed solution (volume ratio of acetic acid and methyl alcohol is 1:9) 200 mL washing earlier, flow rate control is below 1 mL/min, remove acetic acid with 40 mL methanol wash again, put dry 8 h in 80 ℃ of vacuum drying ovens, obtain the molecularly imprinted polymer for detection of the Luo Kesha arsine, put in the moisture eliminator preserve standby.The molecularly imprinted polymer for detection of the Luo Kesha arsine for preparing is compared with synthetic bulk polymer, and average yield reaches 54.2%.
Embodiment 7
Be 54～75 μ m with molecularly imprinted polymer MIP1 and the MIP2(granularities for detection of the Luo Kesha arsine of embodiment 1 and 2 preparations) fill in the empty pillar of 1mL Solid-Phase Extraction (50mg/ post), successively with 2mL methyl alcohol, the activation of 2 mL deionized water balances.
Luo Kesha arsine acetonitrile solution 1 mL that gets 0.5,5,20 and 50 μ g/mL series concentration respectively crosses post, uses 2mL water, 2mL methanol wash successively, press dry, and uses ammoniacal liquor and methyl alcohol mixed liquor (volume ratio of ammoniacal liquor and methyl alcohol is 5:95) 2mL wash-out again.Nitrogen dries up elutriant, and is centrifugal with the potassium dihydrogen phosphate dissolving of 50mmoL/L, uses the high performance liquid chromatography ultraviolet detection.
It is the same that Luo Kesha arsine acetonitrile solution is crossed the operation steps of NIP1 and NIP2 solid-phase extraction column.
Concrete calculate recovery rate process:
Qualitative according to retention time, external standard method is quantitative, measures series concentration (0.5,5,20,50 μ g/mL) Luo Kesha arsine standardized solution response value, and the chromatographic peak integration that obtains gets area A
s, according to the peak area that obtains and concentration C
s, make typical curve as shown in Figure 6, distinguish working sample peak area A again
i, bring typical curve into and calculate, rate of recovery R (%)=100 * C
i/ C
s
Embodiment 8
The molecularly imprinted polymer for detection of the Luo Kesha arsine (granularity is 54～75 μ m) of embodiment 1 preparation is filled in the empty pillar of 1mL Solid-Phase Extraction (50mg/ post), successively with 2mL methyl alcohol, the activation of 2mL water balance.
The Luo Kesha arsine polymer solution in water 1mL that gets 0.5,5,20 and 50 μ g/mL series concentration respectively crosses post, uses 2mL water, 2mL methanol wash successively, press dry, and uses 5% ammoniacal liquor and methyl alcohol mixed liquor (volume ratio of ammoniacal liquor and methyl alcohol is 5:95) 2mL wash-out again.Nitrogen dries up elutriant, and is centrifugal with the potassium dihydrogen phosphate dissolving of 50mmoL/L, uses the high performance liquid chromatography ultraviolet detection.
It is the same that Luo Kesha arsine polymer solution in water is crossed the operation steps of NIP1 solid-phase extraction column.
Underground water and surface water embodiment are except changing Luo Kesha arsine polymer solution in water surface water and the underground water into, and all the other steps are identical.
Fig. 3 crosses the color atlas (5 μ g/mL) of MIP1 and NIP1 solid-phase extraction column for Luo Kesha arsine polymer solution in water; Fig. 4 crosses the color atlas of MIP2 and NIP2 solid-phase extraction column for Luo Kesha arsine surface water solution; Fig. 5 crosses the color atlas of MIP2 and NIP2 solid-phase extraction column for Luo Kesha arsine underground water solution.Table 1 is that MIP, NIP are to the rate of recovery of different concns Luo Kesha arsine in three kinds of water-baseds.The measuring method of the rate of recovery is with embodiment 7.
The different concns Luo Kesha arsine rate of recovery (n=3) in three kinds of water-baseds of table 1
Table 1 is the result show, Luo Kesha arsine water tap water, surface water and the underground water solution of series concentration the rate of recovery on the MIP1, MIP2 solid phase extraction column of preparation all greater than 90%, NIP solid phase extraction column on the rate of recovery all less than 40%.
Embodiment 9
This research adopts static adsorptive method to investigate the adsorption isothermal line of ROX-MIPs.Accurately take by weighing 20.0mgMIP18 part, join in the 25mL Erlenmeyer flask, add the Luo Kesha arsine acetonitrile solution (1,2,5,10,20,50,100,200,300.0 μ g/mL) of 2 mL series concentration again.24h is placed in the room temperature dark place, and 15000rpm is centrifugal, crosses the syringe needle filter membrane, and the free Luo Kesha arsine that does not adsorb in the supernatant liquor is measured with HPLC.Variation according to Luo Kesha arsine concentration in the solution before and after the absorption utilizes formula Q=(C
0-C) V
0/ m calculates the adsorptive capacity of the Luo Kesha arsine of MIPs, and arithmetical av is got in replicate(determination) 3 times, is X-coordinate with Luo Kesha arsine concentration (C), and polymkeric substance equilibrium adsorption capacity (Q) is ordinate zou, draws adsorption isothermal line.C wherein
0Be original concentration (μ g/mL) that C is equilibrium concentration (μ g/mL), m is the quality (g) of imprinted polymer, V
0Be the volume (mL) of adsorbent solution, Q is the micrograms (μ g/g) of the adsorbed Luo Kesha arsine of every gram sorbent material.The adsorption test of NIP1 is except the polymkeric substance difference that takes by weighing, and all the other are the same.Luo Kesha arsine isothermal adsorption line chart as shown in Figure 7, the result shows that MIP1 is 930 μ g/g polymkeric substance in conjunction with the maximal absorptive capacity of Luo Kesha arsine, NIP1 is then below 470 μ g/g polymkeric substance.
Above-described embodiment is preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. preparation method for detection of the molecularly imprinted polymer of Luo Kesha arsine, it is characterized in that: may further comprise the steps: with template, pore-creating agent, function monomer, linking agent and initiator at 50～80 ℃ of polymerization 8～48h, after removing template, namely get for the molecularly imprinted polymer that detects the Luo Kesha arsine; Described template is Pro-gen 90 or ethyl p-hydroxybenzoate.
2. preparation method according to claim 1, it is characterized in that: the ratio of described template, function monomer, linking agent, pore-creating agent and initiator is 1:2～16:10～40 ﹕, 1～200:10～60, and described ratio is mmol:mmol:mmol:mL:mg.
3. preparation method according to claim 1 is characterized in that: described function monomer is 2-vinyl pyridine, methacrylic acid, vinylformic acid, 4-vinylpridine, to Ethenylbenzene formic acid or acrylamide.
4. preparation method according to claim 1, it is characterized in that: described linking agent is ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate or divinylbenzene.
5. preparation method according to claim 1, it is characterized in that: described pore-creating agent is more than one in methyl alcohol, acetonitrile, chloroform, the acetone; Described initiator is water soluble starter or oil-soluble initiator.
6. preparation method according to claim 5, it is characterized in that: described pore-creating agent is acetonitrile; Described oil-soluble initiator is Diisopropyl azodicarboxylate; Described water soluble starter is ammonium persulphate.
7. preparation method according to claim 5, it is characterized in that: described pore-creating agent is that volume ratio is the methyl alcohol of 1:1 and the mixed solution of acetonitrile.
8. preparation according to claim 1 is characterized in that: may further comprise the steps:
(1) preparation of prepolymer: add pore-creating agent in template, vortex to template is dissolved, and adds function monomer, and is ultrasonic, leaves standstill, and obtains prepolymer;
(2) polymerizing curable: in prepolymer, add linking agent and initiator, ultrasonic, logical nitrogen under the ice bath, sealing, polymerization in the vacuum drying oven obtains bulk polymer;
(3) for detection of the preparation of the molecularly imprinted polymer of Luo Kesha arsine: bulk polymer is treated to fine particle, and template is gone in the solvent orange 2 A washing, and after the solvent B washing, vacuum-drying namely gets for the molecularly imprinted polymer that detects the Luo Kesha arsine.
9. preparation method according to claim 8, it is characterized in that: the ultrasonic time described in the step (1) is 5min; Time of repose is 1h;
Ultrasonic time described in the step (2) is 5min; The logical nitrogen time of described ice bath is 5min; The temperature of polymerization is 50～80 ℃ in the described vacuum drying oven, and the time is 8～48h;
Solvent orange 2 A described in the step (3) is the mixing solutions of acetic acid and methyl alcohol, and the volume ratio of acetic acid and methyl alcohol is 1:9 in the mixing solutions; The flow velocity of described solvent orange 2 A washing is below the 1mL/min; Described solvent B is methyl alcohol, and volume is 40mL; Described vacuum drying temperature is 60 ℃, and the time is 12h.
10. the molecularly imprinted polymer for detection of the Luo Kesha arsine for preparing according to each described preparation method of claim 1～9, it is characterized in that: this molecularly imprinted polymer is more than 90% to the rate of recovery of Luo Kesha arsine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310130082.7A CN103232572B (en) | 2013-04-15 | 2013-04-15 | Molecular imprinting polymer for roxarsone detection, and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310130082.7A CN103232572B (en) | 2013-04-15 | 2013-04-15 | Molecular imprinting polymer for roxarsone detection, and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103232572A true CN103232572A (en) | 2013-08-07 |
| CN103232572B CN103232572B (en) | 2015-04-29 |
Family
ID=48880648
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310130082.7A Expired - Fee Related CN103232572B (en) | 2013-04-15 | 2013-04-15 | Molecular imprinting polymer for roxarsone detection, and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103232572B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103992252A (en) * | 2014-05-23 | 2014-08-20 | 华中科技大学 | Dopamine derivative, molecular imprinted polymer and preparation methods and application of dopamine derivative and molecular imprinted polymer |
| CN104193872A (en) * | 2014-08-11 | 2014-12-10 | 江苏大学 | Preparation method and application of porous molecularly-imprinted composite membrane of methyl p-hydroxybenzoate (MICMMP) |
| CN105218746A (en) * | 2014-06-13 | 2016-01-06 | 中国石油化工股份有限公司 | A kind of molecularly imprinted polymer and its preparation method and application |
| CN105566586A (en) * | 2016-03-04 | 2016-05-11 | 中国科学院新疆理化技术研究所 | Preparation method of benzenearsonic acid molecular imprinting polymer |
| CN105572363A (en) * | 2014-10-11 | 2016-05-11 | 江苏维赛科技生物发展有限公司 | ELISA kit for detecting roxarsone, and application thereof |
| CN106323932A (en) * | 2016-10-26 | 2017-01-11 | 武汉大学 | Method for rapidly detecting arsanilic acid and roxarsone in water sample |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101308066A (en) * | 2008-06-12 | 2008-11-19 | 济南大学 | Trace amount mycotoxins molecular blotting column preparation method and application |
| CN102167777A (en) * | 2010-12-22 | 2011-08-31 | 浙江大学 | Preparation method and application of molecularly imprinted polymer |
| CN102520039A (en) * | 2011-12-29 | 2012-06-27 | 济南大学 | Preparation method of aptamer-based molecularly imprinted membrane electrode for detecting organic arsenide in marine products and application |
| CN102519820A (en) * | 2011-12-29 | 2012-06-27 | 济南大学 | Organic arsenide molecularly imprinted membrane substrate in aptamer-based marine products, and production method and application thereof |
-
2013
- 2013-04-15 CN CN201310130082.7A patent/CN103232572B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101308066A (en) * | 2008-06-12 | 2008-11-19 | 济南大学 | Trace amount mycotoxins molecular blotting column preparation method and application |
| CN102167777A (en) * | 2010-12-22 | 2011-08-31 | 浙江大学 | Preparation method and application of molecularly imprinted polymer |
| CN102520039A (en) * | 2011-12-29 | 2012-06-27 | 济南大学 | Preparation method of aptamer-based molecularly imprinted membrane electrode for detecting organic arsenide in marine products and application |
| CN102519820A (en) * | 2011-12-29 | 2012-06-27 | 济南大学 | Organic arsenide molecularly imprinted membrane substrate in aptamer-based marine products, and production method and application thereof |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103992252A (en) * | 2014-05-23 | 2014-08-20 | 华中科技大学 | Dopamine derivative, molecular imprinted polymer and preparation methods and application of dopamine derivative and molecular imprinted polymer |
| CN105218746A (en) * | 2014-06-13 | 2016-01-06 | 中国石油化工股份有限公司 | A kind of molecularly imprinted polymer and its preparation method and application |
| CN105218746B (en) * | 2014-06-13 | 2017-06-30 | 中国石油化工股份有限公司 | A kind of molecularly imprinted polymer and its preparation method and application |
| CN104193872A (en) * | 2014-08-11 | 2014-12-10 | 江苏大学 | Preparation method and application of porous molecularly-imprinted composite membrane of methyl p-hydroxybenzoate (MICMMP) |
| CN105572363A (en) * | 2014-10-11 | 2016-05-11 | 江苏维赛科技生物发展有限公司 | ELISA kit for detecting roxarsone, and application thereof |
| CN105566586A (en) * | 2016-03-04 | 2016-05-11 | 中国科学院新疆理化技术研究所 | Preparation method of benzenearsonic acid molecular imprinting polymer |
| CN105566586B (en) * | 2016-03-04 | 2017-12-19 | 中国科学院新疆理化技术研究所 | A kind of preparation method of arsenobenzene acids molecularly imprinted polymer |
| CN106323932A (en) * | 2016-10-26 | 2017-01-11 | 武汉大学 | Method for rapidly detecting arsanilic acid and roxarsone in water sample |
| CN106323932B (en) * | 2016-10-26 | 2018-10-26 | 武汉大学 | A kind of method of arsanilic acid and roxarsone in quick detection water sample |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103232572B (en) | 2015-04-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103232572B (en) | Molecular imprinting polymer for roxarsone detection, and preparation method thereof | |
| CN102532390B (en) | Triazine weedicide, and metabolite molecular engram polymer microspheres, preparation method and application thereof | |
| CN101864029B (en) | Molecularly imprinted polymer and preparation method and application thereof | |
| CN102600813B (en) | Preparation method and application of surface artemisinin molecule imprinting adsorbing material of vegetable sponge | |
| CN102516679B (en) | Magnetic microsphere resin with high specific surface area and preparation method and application thereof | |
| CN104151489A (en) | Hydrophilic hydroxyl polychlorinated biphenyl molecularly imprinted solid-phase extraction filler as well as preparation method and application thereof | |
| CN103497277B (en) | Scutellarin molecularly imprinted polymer and its preparation method and application | |
| CN101768238A (en) | Citrinin molecular engram material and preparation method as well as application thereof | |
| CN100374860C (en) | Process for producing chloromycetin molecular engram solid phase extraction small column | |
| CN102371084A (en) | Dibutyl phthalate molecularly imprinted polymer (DBP-MIP) solid phase extraction column and preparation method and application thereof | |
| CN102000549B (en) | Preparation method and application of novel melamine molecule imprinting adsorbing material | |
| CN102372821A (en) | Dibutyl phthalate molecularly imprinted polymer (DBP-MIP) and preparation method thereof | |
| CN103908955B (en) | The preparation method of the superhigh cross-linking type polymeric adsorbent that a kind of acetamido is modified and application thereof | |
| CN101649021B (en) | Preparation method and application of molecular imprinting polymer microspheres for Chlorsulfuron | |
| CN101733082A (en) | Method for preparing rhodamine B molecular engram solid phase extraction stuffing and application thereof | |
| CN102731706B (en) | Carbofuran molecularly imprinted microspheres, preparation and application thereof | |
| CN105837747B (en) | A kind of molecular imprinted polymer on surface and its preparation method and application for selective absorption daimeton | |
| CN105675759A (en) | Separation and detection method of BPA (bisphenol A) | |
| CN103554374A (en) | Preparation method and application of surface molecular imprinting solid-phase adsorbent for psychiatric drugs | |
| CN104193875A (en) | Preparation method and application of magnetic diethylstilbestrol molecularly-imprinted polymer | |
| CN104174390B (en) | The preparation method and application of ethopabate molecular imprinted solid phase extraction cartridge | |
| CN103396512A (en) | Hybrid template molecularly imprinted polymer as well as preparation method and application of hybrid template molecularly imprinted solid-phase extraction column | |
| CN105044254A (en) | Method for preparing nitrofuran molecularly imprinted polymer microspheres | |
| CN101921370A (en) | Method for preparing molecularly imprinted polymer used for detecting valnemulin | |
| CN101914066B (en) | Method for purifying and detecting pirimicarb by utilizing molecularly imprinted polymer (MIP) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150429 Termination date: 20210415 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |