CN103232572B - Molecular imprinting polymer for roxarsone detection, and preparation method thereof - Google Patents
Molecular imprinting polymer for roxarsone detection, and preparation method thereof Download PDFInfo
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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 for molecularly imprinted polymer detecting roxarsone and preparation method thereof.
Background technology
Roxarsone (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 adds medicine containing arsenic feed, and roxarsone is applied wider than Pro-gen 90.Roxarsone is the most economical multi-functional organic arsenic of one, has promotion growth of animals or poultry, improves food conversion ratio, and promotes poultry pigment deposition, can increase the effect of other anticoccidial drug to poultry; The dysentery for the treatment of pig and enteritis, improve laying rate of laying hen.The Ministry of Agriculture of China have approved the use of this medicine for 1996, domesticly afterwards starts a large amount of production gradually, and is widely used in poultry husbandry and pig industry.But research afterwards finds that it easily causes environmental pollution, and European Union in 1999 has prohibited and used roxarsone as chicken feed interpolation medicine.Consider animal food safety, the Ministry of Agriculture of China announces No. 235 and has also formulated the maximum residue limit(MRL) of roxarsone.This medical instrument has certain residual toxicity, has potential carinogenicity possibility, therefore its detection is also become rapidly to the focus of research both at home and abroad to the mankind.But the pre-treating process that existing all roxarsones detect is all adopt traditional solid phase extraction column (as MAX) purification, and lack selectivity, specificity is not strong, thus affects sensitivity and the accurate quantitative analysis of whole detection method.
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 as antibody, polymer adsorbing material roxarsone to highly selective of some similar antibody can be synthesized, sensitivity and the accuracy of roxarsone detection greatly can be improved.
Molecular imprinting (molecular imprinting) is the new research field of of developing rapidly based on molecular recognition theory in recent years, and molecular imprinting is also referred to as the technology of manufacture " plastics antibody ".Molecularly imprinted polymer (molecular imprinting polymers, MIP) is that a class inside has the hole of fixed size and shape and has the cross-linked high polymer determining arranging functional group.Because MIP is customized according to microsphere, therefore it has special molecular structure and functional group, optionally can identify microsphere.
The preparation of molecularly imprinted polymer generally will by following three steps:
(1) function monomer is by interacting (covalently or non-covalently key) with template molecule, is gathered in around template molecule and forms reversible mixture;
(2) there is copolymerization and generate superpolymer in function monomer and excess cross-linker under pore-creating agent exists;
(3) dissociate out from superpolymer by template molecule, just defining in the polymer can the binding site of recognition template molecule.
This imprinted polymer can be used as the sensing member and Solid-Phase Extraction material etc. of the stationary phase of liquid chromatography, catalysts selective, chemical sensor, is also widely used in 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 is to provide a kind of preparation method of the molecularly imprinted polymer for detecting roxarsone.This preparation method is with low cost, simple to operate.
Another object of the present invention is to provide the molecularly imprinted polymer for detecting roxarsone prepared by above-mentioned preparation method.This molecularly imprinted polymer has highly selective and affinity to roxarsone, is more than 90% to the rate of recovery of roxarsone.
The object of the invention is to be achieved through the following technical solutions:
A kind of preparation method of the molecularly imprinted polymer for detecting roxarsone, comprise the following steps: by template, pore-creating agent, function monomer, linking agent and initiator at 50 ~ 80 DEG C of polymerization 8 ~ 48 h, after removing template, obtain the molecularly imprinted polymer for detecting roxarsone;
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 ~ 200:10 ~ 60,1:2 ~ 16:10 ~ 40, and described ratio is mmol:mmol:mmol:mL:mg.
Described function monomer be 2-vinyl pyridine, methacrylic acid, vinylformic acid, 4-vinylpridine, to vinylbenzoic 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, acetone; Preferred pore-creating agent is simple acetonitrile or volume ratio is the methyl alcohol of 1:1 and the mixed solution of acetonitrile.Pore-creating agent will ensure the abundant dissolving of template on the one hand, pore-creating agent consumption has material impact to the molecularly imprinted polymer intensity prepared, surface property on the other hand, pore-creating agent is using the identification of roxarsone in medium system also very crucial to imprinted polymer simultaneously, when pore-creating agent selects methanol-acetonitrile (1:1, V/V), time, molecularly imprinted polymer roxarsone to high degree of specificity identification can be prepared.
Described initiator is water soluble starter or oil-soluble initiator; Described oil-soluble initiator is Diisopropyl azodicarboxylate; Described water soluble starter is ammonium persulphate.
For detecting a preparation method for the molecularly imprinted polymer of roxarsone, its preferred concrete steps are:
(1) preparation of prepolymer: add pore-creating agent in template, vortex dissolves to template, adds function monomer, ultrasonic, leaves standstill, obtains prepolymer;
(2) polymerizing curable: add linking agent and initiator in prepolymer, ultrasonic, logical nitrogen under ice bath, sealing, is polymerized in vacuum drying oven, obtains bulk polymer;
(3) for detecting the preparation of the molecularly imprinted polymer of roxarsone: bulk polymer is treated to fine particle, template is gone in solvent orange 2 A washing, and after solvent B washs, vacuum-drying, obtains the molecularly imprinted polymer for detecting roxarsone.
Ultrasonic time described in step (1) is 5min; Time of repose is 1h;
Ultrasonic time described in step (2) is 5min; It is 5min that described ice bath leads to the nitrogen time; The temperature of being polymerized in described vacuum drying oven is 50 ~ 80 DEG C, and the time is 8 ~ 48h.
Solvent orange 2 A described in step (3) is the mixing solutions of acetic acid and methyl alcohol, and in mixing solutions, the volume ratio of acetic acid and methyl alcohol is 1:9; The flow velocity of described solvent orange 2 A washing is below 1mL/min; Described solvent B is methyl alcohol, and volume is 40mL; Described vacuum drying temperature is 60 DEG C, and the time is 12h.
According to the molecularly imprinted polymer for detecting roxarsone that preparation method described above prepares, this molecularly imprinted polymer is more than 90% to the rate of recovery of roxarsone.
Molecularly imprinted polymer of the present invention, finds: this polymkeric substance is used for Solid phase extraction (50mg/ post), polymkeric substance is about 930 μ g/g polymkeric substance in conjunction with the adsorptive capacity of roxarsone after testing; In the aqueous solution (tap water, underground and surface water), add roxarsone recovery test show, within the scope of 1.0 ~ 50 μ g/mL concentration Pitch-based sphere, the roxarsone rate of recovery is greater than 90%; The solid phase extraction column of molecularly imprinted polymer filling of the present invention, after reusing 10 times, the rate of recovery of roxarsone is still greater than 80%.
The present invention has following advantage and effect relative to prior art:
(1) when the present invention prepares molecularly imprinted polymer, the pore-creating agent of employing is methanol-acetonitrile (1:1, V/V), is conducive to the dissolving of template, makes the imprinted polymer specific recognition capability of preparation strong.
(2) preparation method of the present invention directly can add linking agent and initiator and then carries out 50 ~ 80 DEG C of thermopolymerizations solidifications in prepolymer, carry out 50 ~ 80 DEG C of thermopolymerization solidifications after can also first carrying out low temperature photopolymerization again, the specificity of molecularly imprinted polymer can be improved so further.
(3) molecularly imprinted polymer of the present invention presents high affinity and selectivity to roxarsone in methyl alcohol and acetonitrile, and the rate of recovery is greater than 90%.
(4) MIP that the present invention obtains for template with ethyl p-hydroxybenzoate or Pro-gen 90 shows high cross reaction to roxarsone, there is high selectivity and specificity, with with roxarsone this as templated synthesis MIP compared with, can prevent because roxarsone wash-out is incomplete, because " template leakage " in MIP (residual roxarsone template) causes the impact on roxarsone detected result during use, have a wide range of applications as the sample purification pre-treatment material analyzing roxarsone in the matrix such as feed, animal tissues and ambient water.
Accompanying drawing explanation
Fig. 1: roxarsone acetonitrile solution crosses the color atlas (10 μ g/mL) of MIP1 and NIP1 solid-phase extraction column;
Wherein, a: roxarsone acetonitrile solution crosses the color atlas of MIP1 Solid-Phase Extraction; B: roxarsone acetonitrile solution crosses the color atlas of NIP1 Solid-Phase Extraction.
Fig. 2: roxarsone acetonitrile solution crosses the color atlas (10 μ g/mL) of MIP2 and NIP2 solid-phase extraction column;
Wherein, c: roxarsone acetonitrile solution crosses the color atlas of MIP2 Solid-Phase Extraction; D: roxarsone acetonitrile solution crosses the color atlas of NIP2 Solid-Phase Extraction.
Fig. 3: roxarsone polymer solution in water crosses the color atlas (5 μ g/mL) of MIP1 and NIP1 solid-phase extraction column;
Wherein, e: roxarsone polymer solution in water crosses the color atlas of MIP1 solid-phase extraction column; F: roxarsone polymer solution in water crosses the color atlas of NIP1 solid-phase extraction column.
Fig. 4: roxarsone surface water solution crosses the color atlas of MIP2 and NIP2 solid-phase extraction column; (0.5 μ g/mL);
Wherein, g: roxarsone surface water solution crosses the color atlas of MIP1 solid-phase extraction column; H: roxarsone surface water solution crosses the color atlas of NIP1 solid-phase extraction column.
Fig. 5: roxarsone underground water solution crosses the color atlas of MIP2 and NIP2 solid-phase extraction column; (50 μ g/mL);
Wherein, i: roxarsone underground water solution crosses the color atlas of MIP2 solid-phase extraction column; J: roxarsone underground water solution crosses the color atlas of NIP2 solid-phase extraction column.
Fig. 6: the typical curve of the color atlas of roxarsone.
Fig. 7: the sorption isotherm at roxarsone 25 DEG C.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
(1) take 0.166g(1mmoL) ethyl p-hydroxybenzoate in test tube, add 1mL acetonitrile, vortex dissolve after, then add 0.434mL(4mmoL) 2-vinylpyridine function monomer, ultrasonic 5min, leave standstill 1h, formed prepolymer.
(2) in above-mentioned prepolymer, ethylene glycol dimethacrylate 4mL(20mmoL is added) and Diisopropyl azodicarboxylate 60mg (0.365mmol), ultrasonic 5min, logical nitrogen 5min under ice bath, sealing, be polymerized 24h in 60 DEG C of vacuum drying ovens, obtain bulk polymer.
(3) above-mentioned bulk polymer ground, cross 200 mesh sieves, with methyl alcohol sedimentation removing fine particle repeatedly, load in 15mL solid-phase extraction column, acetic acid and methanol mixed solution (volume ratio of acetic acid and methyl alcohol is 1:9) 200mL is first used to wash and remove template ethyl p-hydroxybenzoate, flow rate control is at below 1mL/min, again with 40mL methanol wash removing acetic acid, put dry 12 h in 60 DEG C of vacuum drying ovens, obtaining the molecularly imprinted polymer for detecting roxarsone, putting in moisture eliminator and saving backup.Prepare for detect roxarsone molecularly imprinted polymer (MIP1) compared with the bulk polymer of synthesis, average yield reaches 64.5%.
The preparation of non-imprinted polymer (NIP1), except not adding except template molecule, is prepared all as stated above and processes.
Embodiment 2
(1) take 0.217g(1mmoL) Pro-gen 90 in test tube, add 6mL methanol-acetonitrile solution (volume ratio of methyl alcohol and acetonitrile is 1:1), vortex dissolve after, add 0.434mL(4mmoL) 2-vinylpyridine function monomer, ultrasonic 5min, leaves standstill 1h, forms prepolymer.
(2) in above-mentioned prepolymer, ethylene glycol dimethacrylate 4mL(20mmoL is added) and Diisopropyl azodicarboxylate 60mg (0.365mmol), ultrasonic 5min, logical nitrogen 5min under ice bath, sealing, be polymerized 24h in 60 DEG C of vacuum drying ovens, obtain bulk polymer.
(3) above-mentioned bulk polymer ground, cross 200 mesh sieves, with methyl alcohol sedimentation removing fine particle repeatedly, load in 15mL solid-phase extraction column, acetic acid and methanol mixed solution (volume ratio of acetic acid and methyl alcohol is 1:9) 200mL is first used to wash and remove template Pro-gen 90, flow rate control at below 1mL/min, then with 40mL methanol wash removing acetic acid, puts dry 12 h in 60 DEG C of vacuum drying ovens, obtaining the molecularly imprinted polymer for detecting roxarsone, putting in moisture eliminator and saving backup.Prepare for detect roxarsone molecularly imprinted polymer (MIP2) compared with the bulk polymer of synthesis, average yield reaches 58.2%.
The preparation of non-imprinted polymer (NIP2), except not adding except template molecule, is prepared all as stated above and processes.
Embodiment 3
(1) 0.217g(1mmoL is taken) Pro-gen 90 is in test tube, add 6mL methanol-acetonitrile (1:1, V/V) solution, vortex adds 0.171mL(2mmoL after dissolving) methacrylic acid function monomer, ultrasonic 5min, leaves standstill 1h, forms prepolymer.
(2) in above-mentioned prepolymer, trimethylolpropane trimethacrylate 3.19mL(10mmoL is added) and Diisopropyl azodicarboxylate 10mg(0.06mmoL), ultrasonic 5min, logical nitrogen 5min under ice bath, sealing, be polymerized 48h in 50 DEG C of vacuum drying ovens, obtain bulk polymer.
(3) above-mentioned bulk polymer ground, cross 200 mesh sieves, with methyl alcohol sedimentation removing fine particle repeatedly, load in 15 mL solid-phase extraction columns, first use acetic acid and methanol mixed solution (1:9, V/V) 200mL to wash and remove template Pro-gen 90, flow rate control is at below 1mL/min, again with 40mL methanol wash removing acetic acid, put dry 12h in 60 DEG C of vacuum drying ovens, obtaining the molecularly imprinted polymer for detecting roxarsone, putting in moisture eliminator and saving backup.Prepare for detecting the molecularly imprinted polymer of roxarsone compared with the bulk polymer of synthesis, average yield reaches 52.6%.
Embodiment 4
(1) take 0.166g(1mmoL) ethyl p-hydroxybenzoate in test tube, add 10.5mL acetonitrile, vortex dissolve after, then add 1.82mL(16mmoL) to vinylbenzoic acid function monomer, ultrasonic 5min, leave standstill 1h, formed prepolymer.
(2) in above-mentioned prepolymer, divinylbenzene 5.60mL(40mmoL is added) and Diisopropyl azodicarboxylate 60mg(0.365mmoL), ultrasonic 5min, logical nitrogen 5min under ice bath, sealing, is polymerized 48h in 50 DEG C of vacuum drying ovens, obtains bulk polymer.
(3) above-mentioned bulk polymer ground, cross 200 mesh sieves, with methyl alcohol sedimentation removing fine particle repeatedly, load in 15mL solid-phase extraction column, acetic acid and methanol mixed solution (volume ratio of acetic acid and methyl alcohol is 1:9) 200mL is first used to wash and remove template ethyl p-hydroxybenzoate, flow rate control at below 1mL/min, then with 40mL methanol wash removing acetic acid, puts dry 8h in 80 DEG C of vacuum drying ovens, obtaining the molecularly imprinted polymer for detecting roxarsone, putting in moisture eliminator and saving backup.Prepare for detecting the molecularly imprinted polymer of roxarsone compared with the bulk polymer of synthesis, average yield reaches 48.3%.
Embodiment 5
(1) take 0.217 g(1 mmoL) Pro-gen 90 in test tube, add 9.3 mL methanol-acetonitrile (1:1, V/V) solution, vortex adds 1.42 mL(16 mmoL after dissolving) methacrylic acid function monomer, ultrasonic 5 min, leave standstill 1 h, form prepolymer.
(2) in above-mentioned prepolymer, trimethylolpropane trimethacrylate 12.8 mL(40mmoL is added) and Diisopropyl azodicarboxylate 60mg(0.365mmoL), ultrasonic 5 min, logical nitrogen 5 min under ice bath, sealing, be polymerized 48 h in 50 DEG C of vacuum drying ovens, obtain bulk polymer.
(3) above-mentioned bulk polymer ground, cross 200 mesh sieves, with methyl alcohol sedimentation removing fine particle repeatedly, load in 15 mL solid-phase extraction columns, first use acetic acid and methanol mixed solution (1:9, V/V) 200 mL to wash and remove template Pro-gen 90, flow rate control is at 1 below mL/min, again with 40 mL methanol wash removing acetic acid, put dry 12 h in 60 DEG C of vacuum drying ovens, obtaining the molecularly imprinted polymer for detecting roxarsone, putting in moisture eliminator and saving backup.Prepare for detecting the molecularly imprinted polymer of roxarsone compared with the bulk polymer of synthesis, average yield reaches 46.7%
Embodiment 6
(1) take 0.166g(1 mmoL) ethyl p-hydroxybenzoate in test tube, add 3mL acetonitrile, vortex dissolve after, then add 0.23 mL(2mmoL) to vinylbenzoic acid function monomer, ultrasonic 5 min, leave standstill 1 h, formed prepolymer.
(2) in above-mentioned prepolymer, divinylbenzene 1.4mL(10mmoL is added) and Diisopropyl azodicarboxylate 10mg(0.06 mmoL), ultrasonic 5 min, logical nitrogen 5 min under ice bath, sealing, is polymerized 48 h in 50 DEG C of vacuum drying ovens, obtains bulk polymer.
(3) above-mentioned bulk polymer ground, cross 200 mesh sieves, with methyl alcohol sedimentation removing fine particle repeatedly, load in 15 mL solid-phase extraction columns, acetic acid and methanol mixed solution (volume ratio of acetic acid and methyl alcohol is 1:9) 200 mL are first used to wash and remove template ethyl p-hydroxybenzoate, flow rate control is at 1 below mL/min, again with 40 mL methanol wash removing acetic acid, put dry 8 h in 80 DEG C of vacuum drying ovens, obtaining the molecularly imprinted polymer for detecting roxarsone, putting in moisture eliminator and saving backup.Prepare for detecting the molecularly imprinted polymer of roxarsone compared with the bulk polymer of synthesis, average yield reaches 54.2%.
Embodiment 7
The molecularly imprinted polymer MIP1 being used for detecting roxarsone embodiment 1 and 2 prepared and MIP2(granularity are 54 ~ 75 μm) fill in the empty pillar (50mg/ post) of 1mL Solid-Phase Extraction, successively with 2mL methyl alcohol, 2 mL deionized water balance activation.
Roxarsone acetonitrile solution 1 mL getting 0.5,5,20 and 50 μ g/mL series concentration respectively crosses post, uses 2mL water, 2mL methanol wash successively, press dry, then uses ammoniacal liquor and methyl alcohol mixed liquor (volume ratio of ammoniacal liquor and methyl alcohol is 5:95) 2mL wash-out.Nitrogen dries up elutriant, dissolves with the potassium dihydrogen phosphate of 50mmoL/L, centrifugal, uses high performance liquid chromatography ultraviolet detection.
The operation steps that roxarsone acetonitrile solution crosses NIP1 and NIP2 solid-phase extraction column is the same.
Concrete calculating rate of recovery process:
Qualitative according to retention time, quantified by external standard method, measure series concentration (0.5,5,20,50 μ g/mL) roxarsone standardized solution response value, the chromatography peak integration obtained obtains area A
s, according to the peak area obtained and concentration C
s, make typical curve as shown in Figure 6, then distinguish working sample peak area A
i, bring typical curve into and calculate, rate of recovery R (%)=100 × C
i/ C
s.
Embodiment 8
The molecularly imprinted polymer (granularity is 54 ~ 75 μm) being used for detecting roxarsone embodiment 1 prepared fills in the empty pillar (50mg/ post) of 1mL Solid-Phase Extraction, successively with 2mL methyl alcohol, the activation of 2mL water balance.
The roxarsone polymer solution in water 1mL getting 0.5,5,20 and 50 μ g/mL series concentration respectively crosses post, uses 2mL water, 2mL methanol wash successively, press dry, then uses 5% ammoniacal liquor and methyl alcohol mixed liquor (volume ratio of ammoniacal liquor and methyl alcohol is 5:95) 2mL wash-out.Nitrogen dries up elutriant, dissolves with the potassium dihydrogen phosphate of 50mmoL/L, centrifugal, uses high performance liquid chromatography ultraviolet detection.
The operation steps that roxarsone polymer solution in water crosses NIP1 solid-phase extraction column is the same.
Underground water and surface water embodiment are except changing into except surface water and groundwater by roxarsone polymer solution in water, and all the other steps are identical.
Fig. 3 is the color atlas (5 μ g/mL) that roxarsone polymer solution in water crosses MIP1 and NIP1 solid-phase extraction column; Fig. 4 is the color atlas that roxarsone surface water solution crosses MIP2 and NIP2 solid-phase extraction column; Fig. 5 is the color atlas that roxarsone underground water solution crosses MIP2 and NIP2 solid-phase extraction column.Table 1 is MIP, NIP rate of recovery to different concns roxarsone in three kinds of water-baseds.The measuring method of the rate of recovery, with embodiment 7.
The different concns roxarsone rate of recovery (n=3) in table 1 three kinds of water-baseds
Table 1 result shows, roxarsone water tap water, surface water and groundwater solution rate of recovery on MIP1, MIP2 solid phase extraction column of preparation of series concentration are all greater than the rate of recovery on 90%, NIP solid phase extraction column and are all less than 40%.
Embodiment 9
This research adopts static adsorptive method to investigate the adsorption isothermal line of ROX-MIPs.Accurately take 20.0mgMIP18 part, join in 25mL Erlenmeyer flask, then add the roxarsone acetonitrile solution (1,2,5,10,20,50,100,200,300.0 μ g/mL) of 2 mL series concentration.It is centrifugal that 24h, 15000rpm are placed in room temperature dark place, crosses syringe needle filter membrane, and the free roxarsone HPLC do not adsorbed in supernatant liquor measures.According to the change of roxarsone concentration in solution before and after absorption, utilize formula Q=(C
0-C) V
0/ m calculates MIPs to the adsorptive capacity of roxarsone, and replicate(determination) 3 times, gets arithmetical av, and with roxarsone concentration (C) for X-coordinate, polymkeric substance equilibrium adsorption capacity (Q) is ordinate zou, draws adsorption isothermal line.Wherein C
0for original concentration (μ g/mL), C is equilibrium concentration (μ g/mL), and m is the quality (g) of imprinted polymer, V
0for the volume (mL) of adsorbent solution, the micrograms (μ g/g) of the roxarsone that Q adsorbs for every gram of sorbent material.The adsorption test of NIP1 is except taken polymkeric substance difference, and all the other are the same.As shown in Figure 7, result shows roxarsone isothermal adsorption line chart, and MIP1 is 930 μ g/g polymkeric substance in conjunction with the maximal absorptive capacity of roxarsone, and NIP1 is then below 470 μ g/g polymkeric substance.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (9)
1. one kind for detecting the preparation method of the molecularly imprinted polymer of roxarsone, it is characterized in that: comprise the following steps: by template, pore-creating agent, function monomer, linking agent and initiator at 50 ~ 80 DEG C of polymerization 8 ~ 48 h, after removing template, obtain the molecularly imprinted polymer for detecting roxarsone;
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.
2. preparation method according to claim 1, is characterized in that: described function monomer be 2-vinyl pyridine, methacrylic acid, vinylformic acid, 4-vinylpridine, to vinylbenzoic acid or acrylamide.
3. preparation method according to claim 1, is characterized in that: described linking agent is ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate or divinylbenzene.
4. preparation method according to claim 1, is characterized in that: described pore-creating agent is more than one in methyl alcohol, acetonitrile, chloroform, acetone; Described initiator is water soluble starter or oil-soluble initiator.
5. preparation method according to claim 4, is characterized in that: described pore-creating agent is acetonitrile; Described oil-soluble initiator is Diisopropyl azodicarboxylate; Described water soluble starter is ammonium persulphate.
6. preparation method according to claim 4, is characterized in that: described pore-creating agent is volume ratio is the methyl alcohol of 1:1 and the mixed solution of acetonitrile.
7. preparation method according to claim 1, is characterized in that: comprise the following steps:
(1) preparation of prepolymer: add pore-creating agent in template, vortex dissolves to template, adds function monomer, ultrasonic, leaves standstill, obtains prepolymer;
(2) polymerizing curable: add linking agent and initiator in prepolymer, ultrasonic, logical nitrogen under ice bath, sealing, is polymerized in vacuum drying oven, obtains bulk polymer;
(3) for detecting the preparation of the molecularly imprinted polymer of roxarsone: bulk polymer is treated to fine particle, template is gone in solvent orange 2 A washing, and after solvent B washs, vacuum-drying, obtains the molecularly imprinted polymer for detecting roxarsone.
8. preparation method according to claim 7, is characterized in that: the ultrasonic time described in step (1) is 5min; Time of repose is 1h;
Ultrasonic time described in step (2) is 5min; It is 5min that described ice bath leads to the nitrogen time; The temperature of being polymerized in described vacuum drying oven is 50 ~ 80 DEG C, and the time is 8 ~ 48h;
Solvent orange 2 A described in step (3) is the mixing solutions of acetic acid and methyl alcohol, and in mixing solutions, the volume ratio of acetic acid and methyl alcohol is 1:9; The flow velocity of described solvent orange 2 A washing is 1 below mL/min; Described solvent B is methyl alcohol, and volume is 40mL; Described vacuum drying temperature is 60 DEG C, and the time is 12h.
9. the molecularly imprinted polymer for detecting roxarsone that the preparation method according to any one of claim 1 ~ 8 prepares, is characterized in that: this molecularly imprinted polymer is more than 90% to the rate of recovery of roxarsone.
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| 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 |
| 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 |
| 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 |
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| 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 |
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2013
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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 |
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