CN102911306A - Bisphenol-A and nonylphenol double-template molecularly imprinted polymeric microspheres - Google Patents
Bisphenol-A and nonylphenol double-template molecularly imprinted polymeric microspheres Download PDFInfo
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Abstract
The invention relates to bisphenol-A and nonylphenol double-template molecularly imprinted polymeric microspheres. The bisphenol-A and nonylphenol double-template molecularly imprinted polymeric microspheres are prepared by steps of dissolving nonylphenol and bisphenol-A in chloroform, adding methacrylic acid, performing ultrasonic treatment for 30 minutes, and assembling for 8-12 hours at the temperature of 0-4 DEG C; adding water repellent agents, surfactants, ultrapure water, crosslinking agents and initiators and then mixing; performing ultrasonic treatment for 10-15 minutes, leading in nitrogen gas for 8-15 minutes to remove oxygen, then performing ultrasonic treatment for 10-15 minutes again to form stable emulsion, stirring in water bath at the temperature ranging from 50 DEG C to 100 DEG C, reacting for 5-24 hours to obtain white polymeric microspheres; grinding the polymeric microspheres, extracting in solution composed of methanol and acetic acid at the proportion of 9:1 by means of Soxhlet extraction until no nonylphenol or bisphenol-A is detected by ultraviolet ray, eluting with methanol until the solution is neutral, grinding again and screening, precipitating with acetonitrile, and finally drying in vacuum. The molecularly imprinted polymeric microspheres are high in selectivity, high in adsorption capacity, high in extraction recovery rate and uniform in particle size, and are applicable to enrichment and analysis of bisphenol-A and nonylphenol in aquatic products and samples in water environments.
Description
Technical field
The present invention relates to a kind of dihydroxyphenyl propane and nonyl phenol bimodulus plate molecular blotting polymer microsphere, directly apply to the concentration and analysis of trace amount of bisphenol A and nonyl phenol in fishery products, the environmental sample.
Background technology
Dihydroxyphenyl propane (BisphenolA is called for short BPA) and alkylphenol (Alkylphenols) are the common environmental hormone class of two classes material, because the similarity of structure often is classified as a class research object, are called the phenols environmental estrogens.The research of great many of experiments chamber and environmental surveys result show, the materials such as nonyl phenol (NP) and dihydroxyphenyl propane (BPA) to the increase of the minimizing of mankind spermatozoon quantity, women with breast cancer, uterus carcinoma sickness rate, buck feminize and the decline of birds, fish and Mammals fertility, the part ecosystem in animal female-male proportion imbalance etc. have the effect that can not be ignored, bring serious threat for ecotope and HUMAN HEALTH, thereby become the important substance of the new research of a class and monitoring.
Because BPA, NP are important fine chemical material and intermediates, extensively are present in water body and the organism of ambient soil or rivers and lakes.The content of BPA, NP is extremely low in environmental sample or the organism, adds that sample matrices is complicated, is difficult to direct mensuration, usually needs just can analyze after sample pre-treatments.Therefore, develop the Sample Processes New Method of efficient highly selective significant.
Molecular imprinting (Molecular Imprinting Technique, MIT) is the technology of preparing for the polymkeric substance that obtains to mate fully with certain a part (template molecule) on space structure and binding site.Molecularly imprinted polymer (Molecularly Imprinted Polymer, MIP) because template molecule being had the specificity selective recognition, filler in particular as Solid-Phase Extraction, to realize concentrated, the enrichment to target substance, eliminating the interference of matrix in complicated biological sample or the environmental sample, is an important subject of current sample pre-treatments.
The people such as Xu Jing (polyvinyl chloride, 2010,38 (7): 35-38) take nonyl phenol as template molecule, situ aggregation method prepares the nonyl phenol that molecularly imprinted polymer is used for matrix solid phase dispersion extraction PVC toy and mud, the recovery of extraction 97.8% of n nonylphenol; The people such as Li Yongmin (science and technology and engineering, 2011,11 (25): 6145-6147) utilize molecular imprinting and sol-gel technique, take aminopropyltriethoxywerene werene as function monomer, tetraethoxysilane is linking agent, prepared the nonyl phenol molecular engram material take nonyl phenol as template molecule, the maximum adsorption capacity of polymkeric substance n nonylphenol is 3.85 mg/g; The people such as Guerreiro (Anal. Chim.Acta, 2008,612 (1): 99-104) with computer simulation, nonyl phenol is that the template molecule precipitation polymerization method prepares molecularly imprinted polymer for Solid-Phase Extraction water sample nonyl phenol, and the maximum adsorption capacity of polymkeric substance n nonylphenol is 231 mg/g; People (the J Separation Science such as N ú ez, 2008,31 (13): 2492-2499) adopt one's own department or unit polymerization, prepare molecularly imprinted polymer take toluene as perforating agent and be used for Solid-Phase Extraction complex environment solid sample nonyl phenol and analogue thereof, the rate of recovery 60%～100%.People (the Microchemical Journal such as Surong Mei, 2011,98 (1): 150-155) with the BPA molecular engram solid phase extraction in conjunction with trace BPA in Capillary Electrophoretic Determination river, the well water, the Solid-Phase Extraction rate of recovery does not coexist 71.20%～86.23% because of matrix.The people such as Lin Fuhua (analytical chemistry; 2012,40 (2): 243-248) take BPA as template molecule, utilize the integral material in-situ polymerization technology to prepare molecularly imprinted polymer and be the extraction cake of matrix; be applied to the extraction of water sample BPA, the rate of recovery is 86.2%～112%.The people such as Canale (J Separation Science, 2010,33 (11): 1644-1651) with fluorine bisphenol-a derivative 4,4'-hexafluoro phenol is applied to the Solid-Phase Extraction of BPA in the water sample as the molecularly imprinted polymer of virtual template preparation, and the rate of recovery is greater than 90%.The people such as Jiang Ming (analytical chemistry, 2008,36 (8): 1089-1092) adopt block polymerization, take toluene and whiteruss mixed solvent as pore-creating agent, prepare a kind of dihydroxyphenyl propane molecular engram microsphere, particle diameter 3 μ m.The people such as Xu Zhifeng (Zhongshan University's journal (natural science edition), 2005,44 (3): 53-57) adopt situ aggregation method, do pore-creating agent with toluene, the molecular brand polymer for preparing dihydroxyphenyl propane take dihydroxyphenyl propane as template molecule, binding site is 148.1 μ mol/g (MBPA=228.28 g/mol) to the maximum apparent binding capacity of template molecule.The people such as Yang Benxiao (Nanjing University's journal (natural science), 2007,43 (4): 351-357) adopt mass polymerization, take dihydroxyphenyl propane as template molecule, the 2-vinylpyridine prepares bisphenol A molecular engram polymer as function monomer, poly-trimethylammonium vinylformic acid glycerine ester as linking agent, apparent maximal absorptive capacity is 7. 23 μ mol/g.Su Bo (Donghua University, 2010) uses precipitation polymerization method, and take methacrylic acid (MAA) as function monomer, divinylbenzene (DVB) is for linking agent prepares bisphenol A molecular engram polymer, and maximal absorptive capacity is 606.9 μ mol/g.The people such as Zhao Meiping (SCI; 2003; 24 (7): 1204-1206) adopt situ aggregation method; take dihydroxyphenyl propane as template molecule, methacrylic acid (MAA) is pore-creating agent as function monomer, acetonitrile; Ethylene glycol dimethacrylate is that linking agent prepares bisphenol A molecular engram polymer, is 101.7% to the recovery of extraction of dihydroxyphenyl propane.(Guizhou Education College's journal (natural science), 2008,19 (9): 17-19) adopt the surface molecule print technology, synthesized molecularly imprinted polymer based on dihydroxyphenyl propane at Silica Surface, maximal absorptive capacity is 1.4 μ mol/g to the people such as Zhang Jin.Zhai Meijuan (Nanjing Medical University, 2011) take dihydroxyphenyl propane as template molecule, tetraethyl orthosilicate is linking agent, aminopropyl triethoxysilane is function monomer, by the method for sol-gel polymerizations reaction in silicon-dioxide bead surface reaction last layer molecularly imprinted polymer coating, preparation particle diameter uniform nanometer molecular imprinting polymer is 97% to the recovery of extraction of dihydroxyphenyl propane.
Prior art all is to prepare nonyl phenol molecularly imprinted polymer or bisphenol A molecular engram polymer with nonyl phenol or dihydroxyphenyl propane as single mode plate molecule, employing mostly is mass polymerization and situ aggregation method, the pattern of the polymkeric substance of gained mostly is irregular bulk, though template molecule is shown higher selectivity recognition capability, but loading capacity is low, and the post effect is low.When sample matrices is complicated, often cause template molecule and analog recovery of extraction thereof on the low sidely, lack application prospect.
Summary of the invention
In order to solve the deficiencies in the prior art, the object of the present invention is to provide a kind of dihydroxyphenyl propane and nonyl phenol bimodulus plate molecular blotting polymer microsphere, be that a kind of selectivity and loading capacity are high, particle diameter is than the spherical molecularly imprinted polymer of homogeneous, can be widely used in enrichment, the analysis of dihydroxyphenyl propane and nonyl phenol in fishery products, the environmental water sample, recovery of extraction reaches more than 99%.
Dihydroxyphenyl propane of the present invention and nonyl phenol bimodulus plate molecular blotting polymer microsphere prepare by following steps:
A) 0.2 ~ 2.0 mmol nonyl phenol, 0.2 ~ 2.0 mmol dihydroxyphenyl propane are dissolved in the chloroform, add again 0.8 ~ 8.0 mmol methacrylic acid, ultrasonication 30 minutes, under 0-4 ℃ of temperature self-assembly 8-12 hour;
B) tensio-active agent, 20 ~ 80 mL ultrapure waters, 10.0 ~ 50.0 mmol linking agents and 0.0100 ~ 0.1000 g initiator of adding 0.1 ~ 1.0 mmol hydrophobizing agent, 0.1 ~ 1.0 mmol mix;
C) ultrasonication is 10 ~ 15 minutes, logical nitrogen removed oxygen 8 ~ 15 minutes, ultrasonication is 10 ~ 15 minutes again, utilize ultrasonic wave the material in the solution to be had the characteristics of polymolecularity, form stable emulsion, mechanical stirring in 50 ~ 100 ℃ of water-baths is reacted and was obtained the white polymer microballoon in 5 ~ 24 hours;
D) polymer microballoon that obtains is ground, with volume ratio be 9:1 methyl alcohol-acetic acid solution soxhlet extraction to ultraviolet detection less than nonyl phenol and dihydroxyphenyl propane, be washed till neutrality with methyl alcohol again, grinding is sieved, acetonitrile sedimentation, vacuum-drying obtain dihydroxyphenyl propane and nonyl phenol bimodulus plate molecularly imprinted polymer to constant weight.
According to the further feature of dihydroxyphenyl propane of the present invention and nonyl phenol bimodulus plate molecular blotting polymer microsphere, in the described steps A, the mol ratio of dihydroxyphenyl propane and nonyl phenol is 1:1.
According to the further feature of dihydroxyphenyl propane of the present invention and nonyl phenol bimodulus plate molecular blotting polymer microsphere, in the described steps A, the mol ratio of dihydroxyphenyl propane and methacrylic acid is 1:4.
According to the further feature of dihydroxyphenyl propane of the present invention and nonyl phenol bimodulus plate molecular blotting polymer microsphere, in the described steps A, the mol ratio of nonyl phenol and methacrylic acid is 1:4.
According to the further feature of dihydroxyphenyl propane of the present invention and nonyl phenol bimodulus plate molecular blotting polymer microsphere, among the described step B, the mol ratio of hydrophobizing agent and tensio-active agent is 4:1.
According to the further feature of dihydroxyphenyl propane of the present invention and nonyl phenol bimodulus plate molecular blotting polymer microsphere, among the described step B, the ratio of linking agent and initiator is 400:1(mmol:g).
According to the further feature of dihydroxyphenyl propane of the present invention and nonyl phenol bimodulus plate molecular blotting polymer microsphere, among the described step B, described hydrophobizing agent is selected from: paraffin, n-dodecane, n-tetradecane, n-hexadecane, Octadecane.
Further feature according to dihydroxyphenyl propane of the present invention and nonyl phenol bimodulus plate molecular blotting polymer microsphere, among the described step B, described linking agent is selected from: ethylene glycol dimethacrylate, polyethyleneglycol diacrylate, three methanol-based propane trimethyl acrylic esters (TRIM), first pentaerythritol triacrylate (PETAR), tetramethylol methane tetraacrylate (PETER).
According to the further feature of dihydroxyphenyl propane of the present invention and nonyl phenol bimodulus plate molecular blotting polymer microsphere, among the described step B, described initiator is selected from: Diisopropyl azodicarboxylate (AIBN), Potassium Persulphate, ammonium persulphate, the inferior quadrol of persulphate-tetramethyl-.
Further feature according to dihydroxyphenyl propane of the present invention and nonyl phenol bimodulus plate molecular blotting polymer microsphere, among the described step B, described tensio-active agent is the mixed surfactant that is mixed in the ratio of 1:9 ~ 5:5 by span 80 and cetyl trimethylammonium bromide.
Dihydroxyphenyl propane of the present invention and nonyl phenol bimodulus plate molecular blotting polymer microsphere have following characteristics and advantage: replace single mode plate molecule with bimodulus plate molecule, with function monomer, bimodulus plate molecule (nonyl phenol and dihydroxyphenyl propane) self-assembly in hydrophobic solvent; Hydrophobizing agent (n-tetradecane), tensio-active agent (sorbester p17 and cetyl trimethylammonium bromide) are dissolved in the ultrapure water, make microemulsion; Above-mentioned two kinds of solution are mixed, add linking agent (EDMA) and initiator (AIBN), under magnetic agitation in water-bath thermal initiation, prepare bimodulus plate molecular blotting polymer microsphere by electrostatic interaction, hydrogen bond action.
The prepared imprinted polymer of the present invention has spherical morphology (as shown in Figure 2), particle diameter is than homogeneous (particle diameter is about 0.1 ~ 0.7 μ m), selectivity is high, loading capacity is high (to be measured through Staticadsorption experiment, maximal absorptive capacity to dihydroxyphenyl propane and nonyl phenol is respectively 42.07 mg/g, 23.65 mg/g), recovery of extraction high (take the preparation the imprinted polymer microballoon as solid phase extraction filler, load at methyl alcohol, 2 mL water wash, 6 mL methyl alcohol-acetic acid (9:1, V/V) under the elution requirement, through the Solid-Phase Extraction measuring, recovery of extraction to dihydroxyphenyl propane and nonyl phenol is respectively 99.9% and 98.1%), the preparation method simply waits remarkable advantage, is highly suitable for the concentration and analysis of trace amount of bisphenol A and nonyl phenol in fishery products and the environmental water sample.
Description of drawings
Fig. 1 is the action principle figure that the present invention prepares bimodulus plate molecularly imprinted polymer.
Fig. 2 is the scanning electron microscope (SEM) photograph that the present invention prepares imprinted polymer (MIP).
Fig. 3 is the HPLC color atlas that the present invention measures the Zhaoqing Water of Downstream Xijiang River; Among the figure, (a) undressed Xijiang River water sample; (b) Xijiang River water sample extracts through MIP-SPE; (c) Xijiang River water sample of interpolation 22.03 μ g/L NP, 22.83 μ g/L BPA extracts through MIP-SPE.
Embodiment
Embodiment one: the preparation of dihydroxyphenyl propane of the present invention and nonyl phenol bimodulus plate molecular blotting polymer microsphere
The schematic diagram of the preparation of the described dihydroxyphenyl propane of the present embodiment and nonyl phenol bimodulus plate molecular blotting polymer microsphere as shown in Figure 1, the preparation method may further comprise the steps:
A) 1.0 mmol nonyl phenols, 1.0 mmol dihydroxyphenyl propanes are dissolved in the chloroform 4.0 mmol MAA, ultrasonic 30 minutes, under 0-4 ℃ of temperature self-assembly 8-12 hour;
B) add 0.8 mmol n-tetradecane, 0.2 mmol mixed surfactant, 50 mL ultrapure waters, 20.0 mmol ethylene glycol dimethacrylates (EDMA) and 0.0500 g Diisopropyl azodicarboxylate (AIBN) mix;
C) ultrasonic 10 min, logical nitrogen bubble removing 5 min, ultrasonic 10 min guarantee to form after the emulsion mechanical stirring in 80 ℃ of water-baths again, react 14 h and obtain polymkeric substance, and the pattern of polymkeric substance is as shown in Figure 2;
D) polymkeric substance is ground, with volume ratio be 9:1 methyl alcohol-acetic acid solution soxhlet extraction to ultraviolet detection less than nonyl phenol and dihydroxyphenyl propane, be washed till neutrality with methyl alcohol again, grinding is sieved, acetonitrile sedimentation, vacuum-drying obtain dihydroxyphenyl propane and nonyl phenol bimodulus plate molecularly imprinted polymer to constant weight.
Among the above-mentioned preparation technology, the mixed surfactant that the tensio-active agent that adopts is preferably mixed in the ratio of 3:7 by span 80 and cetyl trimethylammonium bromide (CTAB).
Embodiment two: the preparation of dihydroxyphenyl propane of the present invention and nonyl phenol bimodulus plate molecular blotting polymer microsphere
The schematic diagram of the preparation of the described dihydroxyphenyl propane of the present embodiment and nonyl phenol bimodulus plate molecular blotting polymer microsphere as shown in Figure 1, the preparation method may further comprise the steps:
A) 0.2 mmol nonyl phenol, 0.2 mmol dihydroxyphenyl propane are dissolved in the chloroform 0.8 mmol methacrylic acid (MAA), ultrasonic 30 minutes, under 0-4 ℃ of temperature self-assembly 8-12 hour;
B) add 0.1 mmol paraffin, the inferior quadrol of 0.1 mmol mixed surfactant, 20 mL ultrapure waters, 10.0 mmol polyethyleneglycol diacrylates and 0.0100 g persulphate-tetramethyl-mixes;
C) ultrasonic 12min, logical nitrogen bubble removing 8 min, ultrasonic 12 min guarantee to form after the emulsion mechanical stirring in 50 ℃ of water-baths again, react 5 h and obtain polymkeric substance, and the pattern of polymkeric substance is as shown in Figure 2;
D) polymkeric substance is ground, with volume ratio be 9:1 methyl alcohol-acetic acid solution soxhlet extraction to ultraviolet detection less than nonyl phenol and dihydroxyphenyl propane, be washed till neutrality with methyl alcohol again, grinding is sieved, acetonitrile sedimentation, vacuum-drying obtain dihydroxyphenyl propane and nonyl phenol bimodulus plate molecularly imprinted polymer to constant weight.
Among the above-mentioned preparation technology, the mixed surfactant that the tensio-active agent that adopts is preferably mixed in the ratio of 1:9 by span 80 and cetyl trimethylammonium bromide (CTAB).
Embodiment three: the preparation of dihydroxyphenyl propane of the present invention and nonyl phenol bimodulus plate molecular blotting polymer microsphere
The schematic diagram of the preparation of the described dihydroxyphenyl propane of the present embodiment and nonyl phenol bimodulus plate molecular blotting polymer microsphere as shown in Figure 1, the preparation method may further comprise the steps:
A) 2.0 mmol nonyl phenols, 2.0 mmol dihydroxyphenyl propanes are dissolved in the chloroform 8.0 mmol methacrylic acids (MAA), ultrasonic 30 minutes, under 0-4 ℃ of temperature self-assembly 8-12 hour;
B) add 1.0 mmol n-hexadecanes (or Octadecane), 1.0 mmol mixed surfactants, 80 mL ultrapure waters, 50.0 mmol TRIM(or 40.0 mmol PETAR or PETER) and the mixing of 0. 1000 g Potassium Persulphates (or ammonium persulphate);
C) ultrasonic 15 min, logical nitrogen bubble removing 15 min, ultrasonic 15 min guarantee to form after the emulsion mechanical stirring in 100 ℃ of water-baths again, react 24 h and obtain polymkeric substance, and the pattern of polymkeric substance is as shown in Figure 2;
D) polymkeric substance is ground, with volume ratio be 9:1 methyl alcohol-acetic acid solution soxhlet extraction to ultraviolet detection less than nonyl phenol and dihydroxyphenyl propane, be washed till neutrality with methyl alcohol again, grinding is sieved, acetonitrile sedimentation, vacuum-drying obtain dihydroxyphenyl propane and nonyl phenol bimodulus plate molecularly imprinted polymer to constant weight.
Among the above-mentioned preparation technology, the mixed surfactant that the tensio-active agent that adopts is preferably mixed in the ratio of 5:5 by span 80 and cetyl trimethylammonium bromide (CTAB).
Embodiment four: dihydroxyphenyl propane of the present invention and nonyl phenol bimodulus plate molecularly imprinted polymer are used for the detection of Zhaoqing Xijiang River water sample
Xijiang River water sample (2mL, limit, the Xijiang River, Zhaoqing Duanzhou District Jiang Binsan road) behind the 0.22 μ m filter membrane, directly carries out respectively following two groups of detections: (1) HPLC direct-detection excessively; (2) MIP-SPE-HPLC-FID separation detection, wherein the solid phase extraction filler of separation detection post is prepared dihydroxyphenyl propane and nonyl phenol bimodulus plate molecularly imprinted polymer of embodiment one.
The results are shown in Figure 3.As seen from Figure 3, Xijiang River water sample directly carries out color atlas that HPLC measures (Fig. 3 a) has matrix interference near dihydroxyphenyl propane chromatographic peak (2.587 min); HPLC color atlas (Fig. 3 b) after molecular engram solid phase extraction (MIP-SPE) is processed is not observed obvious Interference Peaks near dihydroxyphenyl propane (2.587 min), nonyl phenol (4.395 min) chromatographic peak; The HPLC color atlas (Fig. 3 c) of the Xijiang River water sample that adds 22.03 μ g/L NP, 22.83 μ g/L BPA after MIP-SPE processes do not have organic interference, at 2.587 min(dihydroxyphenyl propanes), 4.395 min(nonyl phenols) locate to observe obvious chromatographic peak.Molecularly imprinted polymer of the present invention can be used for dihydroxyphenyl propane in the water sample and the detection analysis of nonyl phenol.
Embodiment five: dihydroxyphenyl propane of the present invention and nonyl phenol bimodulus plate molecularly imprinted polymer are used for the detection of beer
After getting the beer sample 2mL that buys in the supermarket and crossing 0.22 μ m filter membrane, directly carry out respectively following two groups of detections: (1) HPLC direct-detection; (2) MIP-SPE-HPLC-FID separation detection, wherein adopt embodiment two prepared dihydroxyphenyl propane and nonyl phenol bimodulus plate molecularly imprinted polymer as the filler of molecular engram solid phase extraction (MIP-SPE).Test result sees Table 1.
The measurement result of BPA and NP (n=3) in table 1 beer sample
| Beer sample | Measured value (μ g/L) | Add scalar (μ g/L) | Average measured value (μ g/L) | Rate of recovery % | RSD % |
| BPA | ND | 22.83 | 22.60 | 99.0 | 4.4 |
| NP | ND | 22.03 | 21.37 | 97.0 | 3.0 |
ND: without detecting.
As can be seen from Table 1, former beer sample can't detect BPA or NP; After in beer sample, adding BPA or NP, the rate of recovery that adopts MIP-SPE-HPLC to detect BPA and NP is respectively 99.0% and 97.0%, RSD is less than 4.4%, illustrate that employing dihydroxyphenyl propane of the present invention and nonyl phenol bimodulus plate molecularly imprinted polymer are as the filler of molecular engram solid phase extraction (MIP-SPE), the absorption rate of recovery for dihydroxyphenyl propane and nonyl phenol is high, goes for the dihydroxyphenyl propane of the drink samples such as beer and the monitoring analysis of nonyl phenol.
Embodiment six: dihydroxyphenyl propane of the present invention and nonyl phenol bimodulus plate molecularly imprinted polymer are used for the detection of crucian
Commercial crucian 7 tails, weight 500 ± 200 g.Wherein 2 tails are done blank fish, and 5 tails are exposed to a week in the Xijiang River water sample that adds nonyl phenol and dihydroxyphenyl propane, carry out toxicological experiment and probe into.Fish is scaled behind the internal organ, get respectively the fish gill, an amount of fish meat sheet is placed in the mincer and smashs to pieces, weigh.25 mL ether extraction, shake 3 h, waste is got the stillness of night, the vortex centrifugal Deproteinization, be dissolved in 5 mL methyl alcohol after nitrogen dries up, carry out molecular engram solid phase extraction (adopting the prepared dihydroxyphenyl propane of embodiment three and nonyl phenol bimodulus plate molecularly imprinted polymer as the filler of molecular engram solid phase extraction (MIP-SPE)), cross 0.22 μ m filter membrane, dilute 10 times and carry out the MIP-SPE-HPLC detection, the results are shown in Table 2.
The measurement result (n=3) of BPA and NP in the commercially available crucian of table 2
ND: without detecting.
As can be seen from Table 2, all do not detect NP in the crucian flesh of fish and the fish gill in the blank group, but all detect BPA; And the rate of recovery that detects BPA and NP in the experimental group is all greater than 96.0%, RSD is less than 5.9%, illustrate that employing dihydroxyphenyl propane of the present invention and nonyl phenol bimodulus plate molecularly imprinted polymer are as the filler of molecular engram solid phase extraction (MIP-SPE), the absorption rate of recovery for dihydroxyphenyl propane and nonyl phenol is high, goes for the dihydroxyphenyl propane of the fishery products such as fish and the monitoring analysis of nonyl phenol.
Claims (10)
1. a dihydroxyphenyl propane and nonyl phenol bimodulus plate molecular blotting polymer microsphere is characterized in that, described polymer microballoon prepares by following steps:
A) 0.2 ~ 2.0 mmol nonyl phenol, 0.2 ~ 2.0 mmol dihydroxyphenyl propane are dissolved in the chloroform, add again 0.8 ~ 8.0 mmol methacrylic acid, ultrasonication 30 minutes, under 0-4 ℃ of temperature self-assembly 8-12 hour;
B) tensio-active agent, 20 ~ 80 mL ultrapure waters, 10.0 ~ 50.0 mmol linking agents and 0.0100 ~ 0.1000 g initiator of adding 0.1 ~ 1.0 mmol hydrophobizing agent, 0.1 ~ 1.0 mmol mix;
C) ultrasonication is 10 ~ 15 minutes, logical nitrogen removed oxygen 8 ~ 15 minutes, ultrasonication is 10 ~ 15 minutes again, utilize ultrasonic wave the material in the solution to be had the characteristics of polymolecularity, form stable emulsion, mechanical stirring in 50 ~ 100 ℃ of water-baths is reacted and was obtained the white polymer microballoon in 5 ~ 24 hours;
D) above-mentioned polymer microballoon is ground, with volume ratio be 9:1 methyl alcohol-acetic acid solution soxhlet extraction to ultraviolet detection less than nonyl phenol and dihydroxyphenyl propane, be washed till neutrality with methyl alcohol again, grinding is sieved, acetonitrile sedimentation, vacuum-drying obtain dihydroxyphenyl propane and nonyl phenol bimodulus plate molecularly imprinted polymer to constant weight.
2. dihydroxyphenyl propane according to claim 1 and nonyl phenol bimodulus plate molecular blotting polymer microsphere, it is characterized in that: in the described steps A, the mol ratio of dihydroxyphenyl propane and nonyl phenol is 1:1.
3. dihydroxyphenyl propane according to claim 1 and nonyl phenol bimodulus plate molecular blotting polymer microsphere, it is characterized in that: in the described steps A, the mol ratio of dihydroxyphenyl propane and methacrylic acid is 1:4.
4. dihydroxyphenyl propane according to claim 1 and nonyl phenol bimodulus plate molecular blotting polymer microsphere, it is characterized in that: in the described steps A, the mol ratio of nonyl phenol and methacrylic acid is 1:4.
5. dihydroxyphenyl propane according to claim 1 and nonyl phenol bimodulus plate molecular blotting polymer microsphere, it is characterized in that: among the described step B, the mol ratio of hydrophobizing agent and tensio-active agent is 4:1.
6. dihydroxyphenyl propane according to claim 1 and nonyl phenol bimodulus plate molecular blotting polymer microsphere, it is characterized in that: among the described step B, the ratio of linking agent and initiator is 400:1(mmol:g).
7. according to claim 1 or 5 dihydroxyphenyl propane and nonyl phenol bimodulus plate molecular blotting polymer microsphere, it is characterized in that: among the described step B, described hydrophobizing agent is selected from: paraffin, n-dodecane, n-tetradecane, n-hexadecane, Octadecane.
8. according to claim 1 or 5 dihydroxyphenyl propane and nonyl phenol bimodulus plate molecular blotting polymer microsphere, it is characterized in that: among the described step B, described tensio-active agent is the mixed surfactant that is mixed in the ratio of 1:9 ~ 5:5 by span 80 and cetyl trimethylammonium bromide.
9. according to claim 1 or 6 described dihydroxyphenyl propanes and nonyl phenol bimodulus plate molecular blotting polymer microsphere, it is characterized in that: among the described step B, described linking agent is selected from: ethylene glycol dimethacrylate, polyethyleneglycol diacrylate, three methanol-based propane trimethyl acrylic esters, first pentaerythritol triacrylate, tetramethylol methane tetraacrylate.
10. according to claim 1 or 6 described dihydroxyphenyl propanes and nonyl phenol bimodulus plate molecular blotting polymer microsphere, it is characterized in that: among the described step B, described initiator is selected from: Diisopropyl azodicarboxylate, Potassium Persulphate, ammonium persulphate, the inferior quadrol of persulphate-tetramethyl-.
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Cited By (4)
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| CN103736468A (en) * | 2014-01-16 | 2014-04-23 | 昆明理工大学 | Preparation method of dual-template molecular imprinting adsorption and extraction stirring rod |
| CN104086795A (en) * | 2014-07-10 | 2014-10-08 | 南京理工大学 | Magnetic molecularly imprinted polymer as well as preparation and application thereof |
| CN105348437A (en) * | 2015-10-27 | 2016-02-24 | 成都市食品药品检验研究院 | Dual-template molecularly imprinted polymer, and preparation method and application thereof |
| CN107840928A (en) * | 2017-11-21 | 2018-03-27 | 石家庄君乐宝乳业有限公司 | The preparation method of nonyl phenol and bisphenol-A double-template molecularly imprinted polymer, nonyl phenol and bisphenol A molecular engram post and its application |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101177500A (en) * | 2007-10-30 | 2008-05-14 | 湖北出入境检验检疫局检验检疫技术中心 | Method for preparing bisphenol A molecular engram polymer |
| CN101857664A (en) * | 2010-06-21 | 2010-10-13 | 湖北出入境检验检疫局检验检疫技术中心 | Preparation method of molecular imprinting polymer with specific recognition capability to tetracycline family |
| US20110026306A1 (en) * | 2006-04-12 | 2011-02-03 | Samsung Electronics Co., Ltd. | Resistance variable memory device reducing word line voltage |
| CN102532390A (en) * | 2011-12-05 | 2012-07-04 | 中国农业科学院农业质量标准与检测技术研究所 | Triazine weedicide, and metabolite molecular engram polymer microspheres, preparation method and application thereof |
| CN102702429A (en) * | 2012-06-19 | 2012-10-03 | 苏州市汉微环保科技有限公司 | Method for preparing bisphenol A molecularly imprinted polymer |
-
2012
- 2012-10-10 CN CN201210381798.XA patent/CN102911306B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110026306A1 (en) * | 2006-04-12 | 2011-02-03 | Samsung Electronics Co., Ltd. | Resistance variable memory device reducing word line voltage |
| CN101177500A (en) * | 2007-10-30 | 2008-05-14 | 湖北出入境检验检疫局检验检疫技术中心 | Method for preparing bisphenol A molecular engram polymer |
| CN101857664A (en) * | 2010-06-21 | 2010-10-13 | 湖北出入境检验检疫局检验检疫技术中心 | Preparation method of molecular imprinting polymer with specific recognition capability to tetracycline family |
| CN102532390A (en) * | 2011-12-05 | 2012-07-04 | 中国农业科学院农业质量标准与检测技术研究所 | Triazine weedicide, and metabolite molecular engram polymer microspheres, preparation method and application thereof |
| CN102702429A (en) * | 2012-06-19 | 2012-10-03 | 苏州市汉微环保科技有限公司 | Method for preparing bisphenol A molecularly imprinted polymer |
Non-Patent Citations (7)
| Title |
|---|
| 《Analytica Chimica Acta》 20050408 Migaku Kawaguchi等 Molecularly imprinted solid phase extraction using stable isotope labeled compounds as template and liquid chromatography-mass spectrometryfor trace analysis of bisphenol A in water sample 第83-89页 1-10 第539卷, * |
| ANTONIO GUERREIRO等: "Preliminary evaluation of new polymer matrix for solid-phase extraction of nonylphenol from water samples", 《ANALYTICA CHIMICA ACTA》, vol. 612, 12 February 2008 (2008-02-12), pages 99 - 104, XP022518173 * |
| MIGAKU KAWAGUCHI等: "Molecularly imprinted solid phase extraction using stable isotope labeled compounds as template and liquid chromatography–mass spectrometryfor trace analysis of bisphenol A in water sample", 《ANALYTICA CHIMICA ACTA》, vol. 539, 8 April 2005 (2005-04-08), pages 83 - 89 * |
| MING JIANG等: "Direct enrichment and high performance liquid chromatography analysis of ultra-trace Bisphenol A in water samples with narrowly dispersibleBisphenol A imprinted polymeric microspheres column", 《JOURNAL OF CHROMATOGRAPHY A》, vol. 1110, 3 February 2006 (2006-02-03), pages 27 - 34 * |
| 徐靖等: "分子印迹基质固相分散-超高效液相色谱法测定儿童玩具中双酚A", 《理化检验-化学分册》, vol. 47, 31 December 2011 (2011-12-31) * |
| 杨本晓等: "双酚A 分子印迹聚合物的制备及其在环境监测中的应用初探", 《河南科学》, vol. 25, no. 6, 31 December 2007 (2007-12-31), pages 1047 - 1051 * |
| 苏博等: "双酚A 分子印迹聚合物的制备及其在水相中的吸附性能", 《化工环保》, vol. 31, no. 2, 31 December 2011 (2011-12-31), pages 167 - 171 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103736468A (en) * | 2014-01-16 | 2014-04-23 | 昆明理工大学 | Preparation method of dual-template molecular imprinting adsorption and extraction stirring rod |
| CN103736468B (en) * | 2014-01-16 | 2016-05-11 | 昆明理工大学 | A kind of preparation method of bimodulus plate molecular imprinting-absorbing extraction stirring rod |
| CN104086795A (en) * | 2014-07-10 | 2014-10-08 | 南京理工大学 | Magnetic molecularly imprinted polymer as well as preparation and application thereof |
| CN105348437A (en) * | 2015-10-27 | 2016-02-24 | 成都市食品药品检验研究院 | Dual-template molecularly imprinted polymer, and preparation method and application thereof |
| CN105348437B (en) * | 2015-10-27 | 2017-11-24 | 成都市食品药品检验研究院 | A kind of double-template molecularly imprinted polymer and preparation method and application |
| CN107840928A (en) * | 2017-11-21 | 2018-03-27 | 石家庄君乐宝乳业有限公司 | The preparation method of nonyl phenol and bisphenol-A double-template molecularly imprinted polymer, nonyl phenol and bisphenol A molecular engram post and its application |
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