CN102580353B - Preparation method of solid phase extraction column of molecular imprinted of phenolic environmental estrogens - Google Patents
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- CN102580353B CN102580353B CN201210041951.4A CN201210041951A CN102580353B CN 102580353 B CN102580353 B CN 102580353B CN 201210041951 A CN201210041951 A CN 201210041951A CN 102580353 B CN102580353 B CN 102580353B
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Abstract
The invention discloses a preparation method of a solid phase extraction column of molecular imprinted of phenolic environmental estrogens. The method comprises steps of: uniformly mixing 100-500mg of molecular imprinted polymer of phenolic environmental estrogens with 5-20mL of pure organic solvent, and uniformly mixing 100-500mg of traditional solid phase extraction packing with 5-20mL of pure organic solvent; orderly moving the mixtures into a hollow solid phase extraction column; plugging two ends of the solid phase extraction column with sieve plates; adding an acid organic solvent into the solid phase extraction column to wash after the solid phase extraction column being uniformly filled; flushing the filled solid phase extraction column with the pure organic solvent; purging the filled solid phase extraction column with inert gases to remove residual organic solvent; and drying to obtain the product. The preparation method disclosed by the invention is simple, and has particularity matching with the molecular imprinted polymer of phenolic environmental estrogens; and the prepared solid phase extraction column performs high selectivity and high recovery rate to the phenolic environmental estrogens, and is capable of obviously reducing the matrix effects.
Description
Technical field
The present invention relates to a kind of preparation method of solid-phase extraction column, relate in particular to a kind of preparation method of solid phase extraction column of molecular imprinted of phenolic environmental estrogens.
Background technology
Phenols environmental estrogens is as the additive of preparing epoxy resin and polycarbonate plastic, enter in organism and can cause endocrinopathy, harm organism Reproductive Performance or initiation malignant tumour, improve the cancer coincidence relevant to hormone, its biological estrogen effect and environmental toxicity have caused domestic and international researcher's extensive concern.Current research shows, the phenols environmental estrogens of the even lower magnitude of 0.1 μ g/L can cause the biological effect of animal used as test, disturb the secretion of endogenous hormone in organism, its low dose effect research has become an important directions of current phenols environmental estrogens research.Given this, carry out the enrichment purification of trace phenols environmental estrogens and detection technique research and be of value to the progress that promotes sanitary inspection technology.
Due to phenols environmental estrogens sample substrate complexity, of a great variety, content is very micro-(pg level), therefore the enrichment purification techniques of sample become its analyze monitoring in committed step.At present, the common method of phenols environmental estrogens sample pretreatment comprises: liquid-liquid extraction and SPE.SPE is higher than liquid-liquid extraction bioaccumulation efficiency, consumption organic solvent is few, simple to operate and be easy to the advantages such as automation.But traditional solid phase extraction column adopts C more
18, the particle such as improved silica, alundum (Al2O3) is as filler, the concentration effect to phenols environmental estrogens and selectively poor.Therefore the solid phase extraction column that, design has high selectivity and high enrichment times to phenols environmental estrogens is of great practical significance for the progress of its enrichment purification and detection technique.
Molecularly imprinted polymer (Molecularly Imprinted Polymers, MIPs) be mainly utilize prepared by molecular imprinting there is can identifying and the special receptor of combining target molecule of high-affinity and high selectivity.MIPs relies on the distribution of shape, size and chemical functional base to identify template molecule, have single-minded selective, because its preparation method is various, technique is relatively easily controlled, specific selectivity strong, predictability, Modulatory character, the Scalability with 26S Proteasome Structure and Function be widely used in the separation and concentration of phenols environmental estrogens in sample.R. Zhu etc. reported (R. Zhu, W. H. Zhao, M. J. Zhai,
et al., Anal. Chim. Acta
2010, 658,209.), take bisphenol-A as template molecule, silica is the nanoscale molecular imprinted polymer for concentration and separation sewage bisphenol-A of carrier.Y. S. Ji etc. reported (Y. S. Ji, J. J. Yin, Z. G. Xu,
et al.,
anal Bioanal Chem. 2009, 395,1125.), take magnetic Nano tri-iron tetroxide as carrier, take bisphenol-A as template molecule, under outside magnetic field effect, can realize the nanometer Fe 3 O 4 magnetic molecularly imprinted polymer of Separation of Solid and Liquid fast and effectively.At present, about the preparation method of solid phase extraction column of molecular imprinted of phenolic environmental estrogens, there is not yet report.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, a kind of preparation method of solid phase extraction column of molecular imprinted of phenolic environmental estrogens is provided.Preparation technology of the present invention is simple, single-minded selectively by force, bioaccumulation efficiency is high; Prepared solid phase extraction column of molecular imprinted of phenolic environmental estrogens has very high selective and extremely strong accumulation ability to trace phenols environmental estrogens residual in water sample and food samples, and can significantly reduce matrix effect.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of preparation method of solid phase extraction column of molecular imprinted of phenolic environmental estrogens, and the method comprises the following steps:
(1) 100 ~ 500mg phenols environmental estrogens molecularly imprinted polymer is mixed with the pure organic solvent of 5 ~ 20mL, after vibration 5 ~ 30min, ultrasonic 5 ~ 30min, to mixing, moves in the solid phase extraction column of the materials such as polypropylene, after filling evenly, sieve plate shutoff is used respectively at two ends.
(2) 100 ~ 500mg tradition solid phase extraction filler is mixed with the pure organic solvent of 5 ~ 20mL, after vibration 5 ~ 30min, ultrasonic 5 ~ 30min is to mixing, move in the solid phase extraction column of step 1, after filling evenly, top sieve plate shutoff, with the acid organic solvent upper prop cleaning of 5 ~ 20mL, then use the pure organic solvent upper prop of 5 ~ 20mL to clean, to remove acidic materials.
(3) solid phase extraction column of step 2 is removed to residual organic solvent by inert gas purge, then 30 ~ 90 ℃ of vacuum drying 1 ~ 24 hour, make solid phase extraction column of molecular imprinted of phenolic environmental estrogens.
The invention has the beneficial effects as follows: the solid phase extraction column of molecular imprinted of phenolic environmental estrogens that the present invention is prepared, have advantages of that preparation technology is simple, single-minded selectively by force, bioaccumulation efficiency is high, and be applied to trace phenols environmental estrogens residual in enrichment Drinking Water and food, higher enrichment times can be reached and matrix effect can be effectively reduced.
Accompanying drawing explanation
Fig. 1 is according to the embodiment of the present invention, obtains multiple-reaction monitoring (MRM) chromatogram of 6 kinds of phenols environmental estrogens, in figure, and (1) bisphenol-A; (2) diethylstilbestrol; (3) hexestrol; (4) the tertiary octyl phenol of 4-; (5) Estradiol Valerate; (6) 4-nonyl phenol.
The specific embodiment
The preparation method of solid phase extraction column of molecular imprinted of phenolic environmental estrogens of the present invention, comprises the following steps:
1,100 ~ 500 mg phenols environmental estrogens molecularly imprinted polymers are mixed with the pure organic solvent of 5 ~ 20 mL, after vibration 5 ~ 30 min, ultrasonic 5 ~ 30 min, to mixing, move in the solid phase extraction column of the materials such as polypropylene, after filling evenly, sieve plate shutoff is used respectively at two ends.
Phenols environmental estrogens molecularly imprinted polymer is preferably Powdered.
Phenols environmental estrogens molecularly imprinted polymer can prepare by following steps:
(1), prepare the monodispersed tri-iron tetroxide/polymer composite microsphere of high magnetic content: adopt chemical coprecipitation to prepare nano ferriferrous oxide particulate, and carry out finishing with oleic acid, then adopt suspension polymerization to prepare the monodispersed tri-iron tetroxide/polymer composite microsphere of high magnetic content;
(2), prepare the recombination reaction liquid of template molecule and amino functional reagent: under 60 ℃ of conditions, in methanol system, template molecule and function base mutually combine through Hyarogen-bonding, form the recombination reaction liquid of template molecule and amino functional group;
(3), preparation amination nanometer Fe 3 O 4 magnetic molecular imprinting composite material: step (1) and step (2) products therefrom carry out surface-functionalized modification through ring-opening reaction to material, finally obtain having the amination nanometer Fe 3 O 4 magnetic molecular imprinting composite material of nucleocapsid structure.
Pure organic solvent can be at least one in methyl alcohol, ethanol, acetonitrile and acetone, more preferably methyl alcohol.
2,100 ~ 500mg tradition solid phase extraction filler is mixed with the pure organic solvent of 5 ~ 20mL, after vibration 5 ~ 30min, ultrasonic 5 ~ 30min is to mixing, move in the solid phase extraction column of step (1), after filling evenly, top sieve plate shutoff, with the acid organic solvent upper prop cleaning of 5 ~ 20mL, then use the pure organic solvent upper prop of 5 ~ 20mL to clean, to remove acidic materials.
Tradition solid phase extraction filler can be C
18, at least one in improved silica, alundum (Al2O3) and PSA, more preferably Powdered C
18.The mass ratio of phenols environmental estrogens molecularly imprinted polymer and traditional solid phase extraction filler is 1:1-1:5.
Acid organic solvent can be at least one and the mixed solution of methyl alcohol, the more preferably mixed solution of formic acid and methyl alcohol in formic acid, acetic acid and trifluoroacetic acid; The volume ratio of formic acid and methyl alcohol is 1:5-1:20.
Pure organic solvent can be at least one in methyl alcohol, ethanol, acetonitrile and acetone, more preferably methyl alcohol.
3, the solid phase extraction column of step 2 is removed to residual organic solvent by inert gas purge, then 30 ~ 90 ℃ of vacuum drying 1 ~ 12 hour, make solid phase extraction column of molecular imprinted of phenolic environmental estrogens.
The performance evaluation of the obtained solid phase extraction column of molecular imprinted of phenolic environmental estrogens of the present invention: by the detection of actual sample is evaluated the performance of solid phase extraction column of molecular imprinted of phenolic environmental estrogens.Adopt methanol-water solution and the formic acid-methanol solution of different proportion to clean solid-phase extraction column, respectively drip washing and elution requirement are optimized, and compare with common SPE post enrichment clean-up effect.Result shows: the obtained solid phase extraction column of molecular imprinted of phenolic environmental estrogens of the present invention is 50-500 times to the enrichment times of target analytes, solid phase extraction column of molecular imprinted of phenolic environmental estrogens is after use 15 times, trace phenols environmental estrogens residual in sample is still had to high selective and accumulation ability, and its rate of recovery is greater than 92.5%.
Below in conjunction with drawings and the specific embodiments, content of the present invention is described further, make advantage of the present invention and beneficial effect more outstanding, but the present invention is not only confined to following examples.
Embodiment 1
The preparation of solid phase extraction column of molecular imprinted of phenolic environmental estrogens:
(1) 100mg phenols environmental estrogens molecularly imprinted polymer is mixed with the pure organic solvent of 10mL, after vibration 10min, ultrasonic 10min, to mixing, moves in the solid phase extraction column of the materials such as polypropylene, and sieve plate shutoff is used respectively at two ends;
(2) 500mg tradition solid phase extraction filler is mixed with the pure organic solvent of 10mL, after vibration 10min, ultrasonic 10min is to mixing, move in step (1) gained solid phase extraction column, top sieve plate shutoff after filling evenly, with the acid organic solvent upper prop cleaning of 10mL, then with the pure organic solvent upper prop of 10mL, clean, to remove acidic materials;
(3) step (2) gained SPE is removed to residual organic solvent by inert gas purge, 30 ℃ of vacuum drying 12 hours, make solid phase extraction column of molecular imprinted of phenolic environmental estrogens.
The performance evaluation of solid phase extraction column of molecular imprinted of phenolic environmental estrogens:
(1) successively with 5mL water and methyl alcohol, solid phase extraction column of molecular imprinted of phenolic environmental estrogens is activated, loading after afterwards 500mL river being filtered, flow velocity is 1.0mL/min, with the mixed solution drip washing of 6mL methyl alcohol and water (1:10 V/V), use again the mixed solution of 10mL methyl alcohol and formic acid (1:10 V/V) to carry out wash-out, eluent blows near dry through nitrogen, dissolves and is settled to 1mL with methyl alcohol, adopts supper-fast liquid chromatography-tandem mass spectrometry instrument (UFLC-MS/MS) to analyze.
(2) successively with 5mL water and methyl alcohol, solid phase extraction column of molecular imprinted of phenolic environmental estrogens is activated, the whole blood sample loading through albumen precipitation by 5mL afterwards, flow velocity is 1.0mL/min, with the mixed solution drip washing of 6mL methyl alcohol and water (1:10 V/V), use again the mixed solution of 10mL methyl alcohol and formic acid (1:10 V/V) to carry out wash-out, eluent blows near dry through nitrogen, dissolve and be settled to 100 μ L with methyl alcohol, adopting supper-fast liquid chromatography-tandem mass spectrometry instrument (UFLC-MS/MS) to analyze.
Embodiment 2 ~ 8 operating procedures are with embodiment 1, and embodiment 1 ~ 8 raw material, composition of raw materials and preparation condition parameter are in Table 1.
Table 1: the embodiment of the present invention 1 ~ 10 raw material components and preparation parameter
The present invention's application solid phase extraction column of molecular imprinted of phenolic environmental estrogens carries out enrichment purification to bisphenol-A, diethylstilbestrol, hexestrol, the tertiary octyl phenol of 4-, Estradiol Valerate and 4-nonyl phenol in water.Accurately take respectively each phenols environmental estrogens standard items 10.0mg in 6 10mL volumetric flasks, after dissolving with a small amount of methyl alcohol, by methanol constant volume, to scale, make the standard reserving solution of 1.0g/L, in 4 ℃ of refrigerators, save backup.Adopting above-mentioned each phenols environmental estrogens standard reserving solution configuration concentration is mixed standard solution 50 ~ 500mL of 0.05 μ g/L, flow velocity is 1.0mL/min, with 6mL methyl alcohol and water (1:10, V/V) mixed solution drip washing, then use the mixed solution of 10mL methyl alcohol and formic acid (1:10, V/V) to carry out wash-out, eluent blows near dry through nitrogen, dissolve and be settled to 1mL with methyl alcohol, adopting supper-fast liquid chromatography-tandem mass spectrometry instrument (UFLC-MS/MS) to analyze, result as shown in Figure 1.Result shows: the solid phase extraction column of molecular imprinted of phenolic environmental estrogens that adopts the present invention to prepare, it is 50 ~ 500 times to the enrichment times of above-mentioned phenols environmental estrogens, is the potential solid-phase extraction column of phenols environmental estrogens in effective enrichment water sample.
chromatographic condition:
Chromatographic column: X-Bridge C
18post (150mm × 2.1mm i.d., 5 μ are m); Flow velocity: 0.4mL/min; Sample size: 5.0 μ L; Mobile phase: A phase: include 0.08% ammoniacal liquor, B phase: include 0.08% ammoniacal liquor methyl alcohol.Gradient elution program: 0 ~ 5.00min, 60.0%A ~ 30.0%A; 5.00 ~ 5.20min, 30%A ~ 10%A; 5.20 ~ 7.00min, 10%A; 7.00 ~ 7.01min, 10.0% A ~ 60.0% A; 7.01 ~ 10.00min, 60.0% A.
mass spectrum condition:
Ion gun: electric spray ion source; Scan mode: anion scanning; Quantitatively detection mode: multiple-reaction monitoring pattern (MRM); Electron spray voltage (IS): 4500V; Atomization gas pressure (GS1): 344.8kPa(50.0psi); Assisted gas flow velocity (GS2): 344.8kPa(50.0psi); Gas curtain atmospheric pressure (CUR): 275.9kPa(40.0psi); Collision gas (CAD): 41.4kPa(6.0psi); Ion source temperature (TEM): 650
oc; Sweep time: 20mS; Collision cell outlet voltage (CXP): 10.0V; Collision cell entrance voltage (EP): 10.0V; Q1/Q3 ion pair, collision energy (CE) and go a bunch voltage (DP) in Table 2.
The Q1/Q3 ion pair of table 2:6 kind phenols environmental estrogens, go a bunch voltage, collision energy and retention time thereof
Note: * quota ion..
Solid phase extraction column of molecular imprinted of phenolic environmental estrogens of the present invention, proves: preparation technology is simple in this invention, with low cost, and the solid phase extraction column of molecular imprinted of phenolic environmental estrogens obtaining is evenly distributed, stable in properties by experiment; Trace amount of bisphenol A residual in water and biological sample, diethylstilbestrol, hexestrol, the tertiary octyl phenol of 4-, Estradiol Valerate and 4-nonyl phenol are had to good enrichment.
Embodiment 9: prepare phenols environmental estrogens molecularly imprinted polymer
1, take respectively 5.56g FeSO
47H
2o and 10.58g FeCl
36H
2o, be dissolved in 200.0mL ultra-pure water, ultrasonic dispersion 5.0 minutes, is heated to 60 ℃, and mixing speed is 300 revs/min, add excessive ammonia to pH be 11.0, constant temperature constant speed reaction 1.0 hours, magnetic separates, successively with ultra-pure water and ethanol washing several to pH be 6-8,60 ℃ of vacuum drying 12 hours, make nano ferriferrous oxide particulate.
2, take nano ferriferrous oxide particulate prepared by 2.0 g steps 1, and joined in 200.0mL ethanolic solution, ultrasonic dispersion 5.0 minutes, constant temperature stirring reaction at 60 ℃, mixing speed is 300 revs/min, in 10 minutes, at the uniform velocity drip 20.0mL oleic acid, react after 1.0 hours, magnetic separates, with ethanol washing for several times to pH be 6-8,60 ℃ of vacuum drying 12 hours, make the nano ferriferrous oxide particulate of surperficial oleic acid modified.
3, take 2.0g polyvinyl alcohol 217 in 500.0mL ultra-pure water, heating for dissolving, using this as dispersant; The nano ferriferrous oxide particulate of oleic acid modified prepared by 1.5 g steps (1) joins in the dispersant of above-mentioned configuration, ultrasonic dispersion 5.0 minutes, by polymerization single polymerization monomer methyl methacrylate (4.0mL), functionalization monomer GMA (4.0mL), crosslinking agent divinylbenzene (2.0mL), under agitation be added drop-wise to successively in reaction system, at 60 ℃, ultrasonic dispersion 5.0 minutes, is uniformly dispersed reaction system.1.0g is crossed to methoxybenzoyl initator to be dissolved in 20.0mL hot ethanol solution, under the rotating speed of 80 ℃, 800 revs/min, be added drop-wise in above-mentioned reaction system, constant temperature constant speed reaction 3.0 hours, magnetic separates, successively with ultra-pure water and ethanol washing for several times, 60 ℃ of vacuum drying 12 hours, make epoxy radicals functionalized nano Fe 3 O 4 magnetic complex microsphere.
4, take respectively 2.0g template molecule and 10.0mL amino functional reagent, and joined in 100.0mL methyl alcohol reaction medium, ultrasonic dispersion 2.0 minutes, under 60 ℃ of conditions, mixing speed is 400 revs/min, temperature constant magnetic stirring reaction 3.0 hours, the recombination reaction liquid of the template molecule of system and amino functional group;
5, take the obtained epoxy radicals functionalized nano of 2.0g step 3 Fe 3 O 4 magnetic complex microsphere, join in the composite micro-emulsion liquid system of the obtained template molecule of step 4 and amino functional group, under the reaction condition of step 4, continue reaction after 8.0 hours, magnetic separates, with ultra-pure water washing for several times to pH be 6-8, be not more detected with methyl alcohol supersound washing several to template molecule, 60 ℃ of vacuum drying 12 hours, make phenols environmental estrogens molecularly imprinted polymer.
Above-mentioned embodiment of the present invention is can not be used for limiting the present invention to explanation of the present invention, and any change in implication and the scope suitable with claims of the present invention, all should think to be included in the scope of claims.
Claims (7)
1. a preparation method for solid phase extraction column of molecular imprinted of phenolic environmental estrogens, is characterized in that, the method comprises the following steps:
(1) 100 ~ 500mg phenols environmental estrogens molecularly imprinted polymer is mixed with the pure organic solvent of 5 ~ 20mL, after vibration 5 ~ 30min, ultrasonic 5 ~ 30min, to mixing, moves in the solid-phase extraction column of polypropylene material, after filling evenly, sieve plate shutoff is used respectively at two ends;
(2) 100 ~ 500mg tradition solid phase extraction filler is mixed with the pure organic solvent of 5 ~ 20mL, after vibration 5 ~ 30min, ultrasonic 5 ~ 30min is to mixing, move in the solid-phase extraction column of step (1), after filling evenly, top sieve plate shutoff, with the acid organic solvent upper prop cleaning of 5 ~ 20mL, then use the pure organic solvent upper prop of 5 ~ 20mL to clean, to remove acidic materials;
(3) solid-phase extraction column of step (2) is removed to residual organic solvent by inert gas purge, then 30 ~ 90 ℃ of vacuum drying 1 ~ 12 hour, make solid phase extraction column of molecular imprinted of phenolic environmental estrogens.
2. preparation method according to claim 1, is characterized in that, in described step (1) and (2), described pure organic solvent is at least one in methyl alcohol, ethanol, acetonitrile and acetone.
3. preparation method according to claim 2, is characterized in that, described pure organic solvent is methyl alcohol.
4. preparation method according to claim 1, is characterized in that, in described step (2), described traditional solid phase extraction filler is C
18, at least one in improved silica, alundum (Al2O3); The mass ratio of described phenols environmental estrogens molecularly imprinted polymer and traditional solid phase extraction filler is 1:1-1:5.
5. preparation method according to claim 4, is characterized in that, described traditional solid phase extraction filler is Powdered C
18.
6. preparation method according to claim 1, is characterized in that, in described step (2), described acid organic solvent is at least one and the mixed solution of methyl alcohol in formic acid, acetic acid and trifluoroacetic acid.
7. preparation method according to claim 6, is characterized in that, described acid organic solvent is the mixed solution of formic acid and methyl alcohol; The volume ratio of formic acid and methyl alcohol is 1:5-1:20.
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| CN103881000A (en) * | 2014-03-20 | 2014-06-25 | 南京大学 | Monodisperse high-specific-surface-area online solid-phase extraction (SPE) column and preparation method thereof |
| CN105688444A (en) * | 2014-11-27 | 2016-06-22 | 宁波市疾病预防控制中心 | Chlorophenol graphene-based molecularly imprinted solid-phase extraction column and preparation method and application thereof |
| CN104707584A (en) * | 2015-02-12 | 2015-06-17 | 宁波市疾病预防控制中心 | Preparation method for molecularly imprinted solid-phase extraction columns of anthraquinone sensitizing disperse dyes |
| CN107907614A (en) * | 2017-12-18 | 2018-04-13 | 丽水学院 | A kind of molecular engram solid phase extraction high performance liquid chromatography tandem mass spectrum assay method of bisphenol compound |
| CN108519445B (en) * | 2018-02-11 | 2020-11-24 | 桂林理工大学 | Method for separating and enriching trace estrogen in environmental water sample |
| CN110585758B (en) * | 2019-09-18 | 2021-10-19 | 昆明理工大学 | Construction method of selectable array type analysis platform based on solid-phase microextraction of various template molecularly imprinted polymers |
| CN111228855A (en) * | 2020-01-14 | 2020-06-05 | 无锡市疾病预防控制中心 | Preparation method of pineapple pulp matrix biochar filler solid-phase extraction column |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1601272A (en) * | 2004-10-26 | 2005-03-30 | 湖南纽尔科技有限公司 | Ethylene equol molecular engram solid phase extracting small pole and its its prepn process |
| CN101661021A (en) * | 2009-08-11 | 2010-03-03 | 上海谱尼测试技术有限公司 | Method for detecting content of bisphenol A |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1601272A (en) * | 2004-10-26 | 2005-03-30 | 湖南纽尔科技有限公司 | Ethylene equol molecular engram solid phase extracting small pole and its its prepn process |
| CN101661021A (en) * | 2009-08-11 | 2010-03-03 | 上海谱尼测试技术有限公司 | Method for detecting content of bisphenol A |
Non-Patent Citations (4)
| Title |
|---|
| Molecularly imprinted layer-coated silica nanoparticles for selective solid-phase extraction of bisphenol A from chemical cleansing and cosmetics samples;Rong Zhu;《Analytica Chimica Acta》;20101231;209-216 * |
| Rong Zhu.Molecularly imprinted layer-coated silica nanoparticles for selective solid-phase extraction of bisphenol A from chemical cleansing and cosmetics samples.《Analytica Chimica Acta》.2010,209-216. |
| 分子印迹技术在环境雌激素检测中的应用;王硕;《食品与生物技术学报》;20071130;99-104 * |
| 王硕.分子印迹技术在环境雌激素检测中的应用.《食品与生物技术学报》.2007,99-104. |
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