CN102580353A - Preparation method of solid phase extraction column of molecular imprinted of phenolic environmental estrogens - Google Patents
Preparation method of solid phase extraction column of molecular imprinted of phenolic environmental estrogens Download PDFInfo
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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 phenols environmental estrogens molecularly imprinted solid phase extraction column.
Background technology
The phenols environmental estrogens is as the additive of preparation epoxy resin and polycarbonate plastic; Get in the organism and can cause endocrinopathy; Harm organism reproduction function or initiation malignant tumour; Improve the cancer coincidence relevant with hormone, its biological estrogen effect and environmental toxicity have caused domestic and international researcher's extensive concern.Current research shows; 0.1 the phenols environmental estrogens of μ g/L even lower magnitude can cause the biological effect of animal used as test; Disturb the secretion of endogenous hormone in the organism, its low dosage effect study has become an important directions of current phenols environmental estrogens research.Given this, enrichment purification and the detection technique research of carrying out trace phenols environmental estrogens are of value to and promote the sanitary inspection development of technology.
Because phenols environmental estrogens sample substrate is complicated, of a great variety, content is very little (pg level), so the sample enrichment purification techniques becomes the committed step in its analysis monitoring.At present, the common method of phenols environmental estrogens sample pretreatment comprises: liquid-liquid extraction and SPE.SPE is higher than the liquid-liquid extraction bioaccumulation efficiency, consume organic solvent lack, simple to operate and be easy to advantage such as automation.Yet traditional solid phase extraction column adopts C more
18, particle such as improved silica, alundum (Al is as filler, and is relatively poor to the concentration effect and the selectivity of phenols environmental estrogens.Therefore, design solid phase extraction column that the phenols environmental estrogens is had high selectivity and a high enrichment multiple is of great practical significance for the progress of its enrichment purification and detection technique.
Molecularly imprinted polymer (Molecularly Imprinted Polymers, MIPs) mainly be utilize molecular imprinting preparation have high-affinity and a high selectivity can discern the special receptor with the combining target molecule.MIPs relies on the distribution of shape, size and chemical functional base that template molecule is discerned; Have single-minded selectivity, various because of its preparation method, technology is relatively easily controlled, specific selectivity is strong, have the expection property of 26S Proteasome Structure and Function, the separation and concentration that Modulatory character cutting property is widely used in phenols environmental estrogens in the sample.R. Zhu etc. reported (R. Zhu, W. H. Zhao, M. J. Zhai,
Et al., Anal. Chim. Acta
2010, 658,209.), be that template molecule, silica are the nanoscale molecular imprinted polymer that is used for concentration and separation sewage bisphenol-A of carrier with the bisphenol-A.Y. S. Ji etc. reported (Y. S. Ji, J. J. Yin, Z. G. Xu,
Et al.,
Anal Bioanal Chem. 2009, 395,1125.), be carrier with the magnetic Nano tri-iron tetroxide, with the bisphenol-A template molecule, the 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 down.At present, the preparation method about phenols environmental estrogens molecularly imprinted solid phase extraction column does not appear in the newspapers as yet.
Summary of the invention
The objective of the invention is to deficiency, a kind of preparation method of phenols environmental estrogens molecularly imprinted solid phase extraction column is provided to prior art.Simple, the single-minded selectivity of preparation technology of the present invention is strong, bioaccumulation efficiency is high; Prepared phenols environmental estrogens molecularly imprinted solid phase extraction column has very high selectivity and extremely strong accumulation ability to trace phenols environmental estrogens residual in water sample and the food samples, and can significantly reduce matrix effect.
In order to solve the problems of the technologies described above, the technical scheme that the present invention adopts is following: a kind of preparation method of phenols environmental estrogens molecularly imprinted solid phase extraction column, and this method may further comprise the steps:
(1) 100 ~ 500mg phenols environmental estrogens molecularly imprinted polymer is mixed with the pure organic solvent of 5 ~ 20mL; Behind vibration 5 ~ 30min, ultrasonic 5 ~ 30min is to mixing, and moves in the solid phase extraction column of material such as polypropylene; After the filling evenly, the sieve plate shutoff is used at two ends respectively.
(2) 100 ~ 500mg tradition solid phase extraction filler is mixed with the pure organic solvent of 5 ~ 20mL, behind vibration 5 ~ 30min, ultrasonic 5 ~ 30min is to mixing; Move in the solid phase extraction column of step 1; After the filling evenly, the sieve plate shutoff is used on the top, cleans with the acid organic solvent upper prop of 5 ~ 20mL; Use the pure organic solvent upper prop of 5 ~ 20mL to clean then, to remove acidic materials.
(3) solid phase extraction column of step 2 is removed residual organic solvent with inert gas purge, 30 ~ 90 ℃ of vacuum drying are 1 ~ 24 hour then, make phenols environmental estrogens molecularly imprinted solid phase extraction column.
The invention has the beneficial effects as follows: the phenols environmental estrogens molecularly imprinted solid phase extraction column that the present invention is prepared; Has the advantage that simple, the single-minded selectivity of preparation technology is strong, bioaccumulation efficiency is high; And be applied to trace phenols environmental estrogens residual in enrichment Drinking Water and the food, higher enrichment multiple can be reached and matrix effect can be effectively reduced.
Description of drawings
Fig. 1 is according to the embodiment of the invention, obtains multiple-reaction monitoring (MRM) chromatogram of 6 kinds of phenols environmental estrogens, among the figure, and (1) bisphenol-A; (2) diethylstilbestrol; (3) hexestrol; (4) uncle's 4-octyl phenol; (5) Estradiol Valerate; (6) 4-nonyl phenol.
The specific embodiment
The preparation method of phenols environmental estrogens molecularly imprinted solid phase extraction column of the present invention may further comprise the steps:
1,100 ~ 500 mg phenols environmental estrogens molecularly imprinted polymers is mixed with the pure organic solvent of 5 ~ 20 mL; Behind vibration 5 ~ 30 min, ultrasonic 5 ~ 30 min are to mixing, and move in the solid phase extraction column of material such as polypropylene; After the filling evenly, the sieve plate shutoff is used at two ends respectively.
Phenols environmental estrogens molecularly imprinted polymer is preferably Powdered.
Phenols environmental estrogens molecularly imprinted polymer can prepare through following steps:
(1), the monodispersed tri-iron tetroxide/polymer composite microsphere of preparation high magnetic content: adopt chemical coprecipitation to prepare the nano ferriferrous oxide particulate; And carry out finishing with oleic acid, adopt suspension polymerization to prepare the monodispersed tri-iron tetroxide/polymer composite microsphere of high magnetic content then;
(2), the recombination reaction liquid of preparation template molecule and amino functional reagent: under 60 ℃ of conditions, in methanol system, template molecule and functional group mutually combine through hydrogen bond action power, form the recombination reaction liquid of template molecule and amino functional group;
(3), preparation amination nanometer Fe 3 O 4 magnetic molecular engram composite: 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 engram composite of nucleocapsid structure.
Pure organic solvent can be at least a in methyl alcohol, ethanol, acetonitrile and the acetone, further is preferably methyl alcohol.
2,100 ~ 500mg tradition solid phase extraction filler is mixed with the pure organic solvent of 5 ~ 20mL, behind vibration 5 ~ 30min, ultrasonic 5 ~ 30min is to mixing; Move in the solid phase extraction column of step (1); After the filling evenly, the sieve plate shutoff is used on the top, cleans with the acid organic solvent upper prop of 5 ~ 20mL; Use the pure organic solvent upper prop of 5 ~ 20mL to clean then, to remove acidic materials.
The tradition solid phase extraction filler can be C
18, at least a among improved silica, alundum (Al and the PSA, further be preferably Powdered C
18The 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 the mixed solution of at least a and methyl alcohol in formic acid, acetate and the trifluoroacetic acid, further is preferably the mixed solution of formic acid and methyl alcohol; The volume ratio of formic acid and methyl alcohol is 1:5-1:20.
Pure organic solvent can be at least a in methyl alcohol, ethanol, acetonitrile and the acetone, further is preferably methyl alcohol.
3, the solid phase extraction column of step 2 is removed residual organic solvent with inert gas purge, 30 ~ 90 ℃ of vacuum drying are 1 ~ 12 hour then, make phenols environmental estrogens molecularly imprinted solid phase extraction column.
The performance evaluation of the obtained phenols environmental estrogens of the present invention molecularly imprinted solid phase extraction column: the detection through to actual sample is estimated the performance of phenols environmental estrogens molecularly imprinted solid phase extraction column.Adopt the methanol-water solution and the formic acid-methanol solution of different proportion that solid-phase extraction column is cleaned, respectively drip washing and elution requirement are optimized, and compare with common SPE post enrichment clean-up effect.The result shows: the obtained phenols environmental estrogens of the present invention molecularly imprinted solid phase extraction column is 50-500 times to the enrichment multiple of target analytes; Phenols environmental estrogens molecularly imprinted solid phase extraction column is using after 15 times; Trace phenols environmental estrogens to residual in the sample still has high selectivity and accumulation ability, and its rate of recovery is greater than 92.5%.
Below in conjunction with accompanying drawing and specific embodiment content of the present invention is further specified, make advantage of the present invention and beneficial effect more outstanding, but the present invention not only is confined to following examples.
Embodiment 1
The preparation of phenols environmental estrogens molecularly imprinted solid phase extraction column:
(1) 100mg phenols environmental estrogens molecularly imprinted polymer is mixed with the pure organic solvent of 10mL, ultrasonic 10min moves in the solid phase extraction column of material such as polypropylene to mixing behind the vibration 10min, and the sieve plate shutoff is used at two ends respectively;
(2) 500mg tradition solid phase extraction filler is mixed with the pure organic solvent of 10mL; Ultrasonic 10min is to mixing behind the vibration 10min; Move in step (1) the gained solid phase extraction column, filling is evenly used the sieve plate shutoff in the top, back, cleans with the acid organic solvent upper prop of 10mL; Clean with the pure organic solvent upper prop of 10mL then, to remove acidic materials;
(3) step (2) gained SPE is removed residual organic solvent with inert gas purge, 30 ℃ of vacuum drying 12 hours make phenols environmental estrogens molecularly imprinted solid phase extraction column.
The performance evaluation of phenols environmental estrogens molecularly imprinted solid phase extraction column:
(1) successively phenols environmental estrogens molecularly imprinted solid phase extraction column is carried out activation with 5mL water and methyl alcohol; Afterwards the 500mL river is filtered the back and go up appearance, flow velocity is 1.0mL/min, with the mixed solution drip washing of 6mL methyl alcohol and water (1:10 V/V); Use the mixed solution of 10mL methyl alcohol and formic acid (1:10 V/V) to carry out wash-out again; Eluent blows near through nitrogen to be done, and with the methyl alcohol dissolving and be settled to 1mL, adopts supper-fast liquid chromatography-tandem mass spectrometry appearance (UFLC-MS/MS) to analyze.
(2) successively phenols environmental estrogens molecularly imprinted solid phase extraction column is carried out activation with 5mL water and methyl alcohol; Afterwards with 5mL appearance on the whole blood sample of albumen precipitation; Flow velocity is 1.0mL/min; With the mixed solution drip washing of 6mL methyl alcohol and water (1:10 V/V), use the mixed solution of 10mL methyl alcohol and formic acid (1:10 V/V) to carry out wash-out again, eluent blows near through nitrogen to be done; With methyl alcohol dissolving and be settled to 100 μ L, adopt supper-fast liquid chromatography-tandem mass spectrometry appearance (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 seen table 1.
Table 1: the embodiment of the invention 1 ~ 10 raw material components and preparation parameter
The present invention uses phenols environmental estrogens molecularly imprinted solid phase extraction column bisphenol-A, diethylstilbestrol, hexestrol, uncle's 4-octyl phenol, Estradiol Valerate and 4-nonyl phenol in the water is carried out the enrichment purification.Accurately take by weighing each phenols environmental estrogens standard items 10.0mg respectively in 6 10mL volumetric flasks, after the small amount of methanol dissolving, to scale, process the standard reserving solution of 1.0g/L, in 4 ℃ of refrigerators, preserve subsequent use with methanol constant volume.Adopting above-mentioned each phenols environmental estrogens standard reserving solution configuration concentration is mixed standard solution 50 ~ 500mL of 0.05 μ g/L, and flow velocity is 1.0mL/min, with 6mL methyl alcohol and water (1:10; V/V) mixed solution drip washing, use again 10mL methyl alcohol and formic acid (1:10, mixed solution V/V) carries out wash-out; Eluent blows near through nitrogen to be done; With methyl alcohol dissolving and be settled to 1mL, adopt supper-fast liquid chromatography-tandem mass spectrometry appearance (UFLC-MS/MS) to analyze, the result is as shown in Figure 1.The result shows: adopt the phenols environmental estrogens molecularly imprinted solid phase extraction column of the present invention's preparation, its enrichment multiple to above-mentioned phenols environmental estrogens is 50 ~ 500 times, 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 m); Flow velocity: 0.4mL/min; Sample size: 5.0 μ L; Flowing phase: A phase: include 0.08% ammoniacal liquor, the 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.
The mass spectrum condition:
Ion gun: electric spray ion source; Scan mode: anion scanning; Detection by quantitative mode: multiple-reaction monitoring pattern (MRM); Electron spray voltage (IS): 4500V; Atomization gas pressure (GS1): 344.8kPa (50.0psi); Secondary air speed (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 inlet voltage (EP): 10.0V; Q1/Q3 ion pair, collision energy (CE) and go a bunch voltage (DP) to see 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
Annotate: the * quota ion..
Phenols environmental estrogens molecularly imprinted solid phase extraction column according to the invention proves through experiment: preparation technology is simple, with low cost in this invention, and the phenols environmental estrogens molecularly imprinted solid phase extraction column that obtains is evenly distributed stable in properties; Trace amount of bisphenol A residual in water and the biological sample, diethylstilbestrol, hexestrol, uncle's 4-octyl phenol, Estradiol Valerate and 4-nonyl phenol had good enrichment.
Embodiment 9: preparation phenols environmental estrogens molecularly imprinted polymer
1, takes by weighing 5.56g FeSO respectively
47H
2O and 10.58g FeCl
36H
2O is dissolved in the 200.0mL ultra-pure water, ultrasonic dispersion 5.0 minutes; Heat temperature raising to 60 ℃, mixing speed is 300 rev/mins, add excessive ammonia to pH be 11.0; Constant temperature constant speed reaction 1.0 hours, magnetic separates, and successively uses ultra-pure water and washing with alcohol several to be 6-8 to pH; 60 ℃ of vacuum drying 12 hours make the nano ferriferrous oxide particulate.
2, take by weighing the nano ferriferrous oxide particulate of 2.0 g steps 1 preparation, and it is joined in the 200.0mL ethanolic solution ultrasonic dispersion 5.0 minutes; At 60 ℃ of following constant temperature stirring reactions, mixing speed is 300 rev/mins, at the uniform velocity drips 20.0mL oleic acid in 10 minutes; React after 1.0 hours, magnetic separates, and uses the washing with alcohol several to be 6-8 to pH; 60 ℃ of vacuum drying 12 hours make the nano ferriferrous oxide particulate of surperficial oleic acid modified.
3, take by weighing 2.0g polyvinyl alcohol 217 in the 500.0mL ultra-pure water, heating for dissolving, with this as dispersant; The nano ferriferrous oxide particulate of the oleic acid modified of 1.5 g steps (1) preparations is joined in the dispersant of above-mentioned configuration; Ultrasonic dispersion 5.0 minutes; With 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 the reaction system, 60 ℃ are descended ultrasonic dispersion 5.0 minutes, reaction system are uniformly dispersed.1.0g is crossed the methoxybenzoyl initator to be dissolved in the 20.0mL hot ethanol solution; Under 80 ℃, 800 rev/mins rotating speed, be added drop-wise in the above-mentioned reaction system constant temperature constant speed reaction 3.0 hours; Magnetic separates; Successively with ultra-pure water and washing with alcohol several, 60 ℃ of vacuum drying 12 hours make epoxy radicals functionalized nano Fe 3 O 4 magnetic complex microsphere.
4, take by weighing 2.0g template molecule and 10.0mL amino functional reagent respectively; And it is joined in the 100.0mL methyl alcohol reaction medium; Ultrasonic dispersion 2.0 minutes, under 60 ℃ of conditions, mixing speed is 400 rev/mins; Constant temperature magnetic agitation reaction 3.0 hours, the recombination reaction liquid of the template molecule of system and amino functional group;
5, take by weighing 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 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, and uses the ultra-pure water washing to be 6-8 to pH for several times, is not detected with methyl alcohol supersound washing several to template molecule again; 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 to limit the present invention to explanation of the present invention, and implication suitable with claims of the present invention and any change in the scope all should be thought to be included in the scope of claims.
Claims (7)
1. the preparation method of a phenols environmental estrogens molecularly imprinted solid phase extraction column is characterized in that, this method may further comprise the steps:
(1) 100 ~ 500mg phenols environmental estrogens molecularly imprinted polymer is mixed with the pure organic solvent of 5 ~ 20mL; Behind vibration 5 ~ 30min, ultrasonic 5 ~ 30min is to mixing, and moves in the SPE void column of material such as polypropylene; After the filling evenly, the sieve plate shutoff is used at two ends respectively;
(2) 100 ~ 500mg tradition solid phase extraction filler is mixed with the pure organic solvent of 5 ~ 20mL, behind vibration 5 ~ 30min, ultrasonic 5 ~ 30min is to mixing; Move in the solid phase extraction column of step 1; After the filling evenly, the sieve plate shutoff is used on the top, cleans with the acid organic solvent upper prop of 5 ~ 20mL; Use the pure organic solvent upper prop of 5 ~ 20mL to clean then, to remove acidic materials;
(3) solid phase extraction column of step 2 is removed residual organic solvent with inert gas purge, 30 ~ 90 ℃ of vacuum drying are 1 ~ 12 hour then, make phenols environmental estrogens molecularly imprinted solid phase extraction column.
2. preparation method according to claim 1 is characterized in that, in said step (1) and (2), said pure organic solvent can be at least a in methyl alcohol, ethanol, acetonitrile and the acetone.
3. preparation method according to claim 2 is characterized in that, said pure organic solvent is preferably methyl alcohol.
4. preparation method according to claim 1 is characterized in that, in the said step (2), said traditional solid phase extraction filler can be C
18, at least a among improved silica, alundum (Al and the PSA; The mass ratio of said 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, said traditional solid phase extraction filler further is preferably Powdered C
18
6. preparation method according to claim 1 is characterized in that, in the said step (2), said acid organic solvent can be the mixed solution of at least a and methyl alcohol in formic acid, acetate and the trifluoroacetic acid.
7. preparation method according to claim 6 is characterized in that said acid organic solvent further is preferably 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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| 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 |
| WO2015139462A1 (en) * | 2014-03-20 | 2015-09-24 | 南京大学 | On-line solid-phase extraction column with mono-dispersion and high specific surface area and preparation method therefor |
| 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 |
| 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 |
| CN108519445A (en) * | 2018-02-11 | 2018-09-11 | 桂林理工大学 | A kind of method of trace estrogen in separation and concentration environmental water sample |
| CN110585758A (en) * | 2019-09-18 | 2019-12-20 | 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 |
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| WO2015139462A1 (en) * | 2014-03-20 | 2015-09-24 | 南京大学 | On-line solid-phase extraction column with mono-dispersion and high specific surface area and preparation method therefor |
| 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 |
| CN108519445A (en) * | 2018-02-11 | 2018-09-11 | 桂林理工大学 | A kind of method of trace estrogen in separation and concentration environmental water sample |
| CN110585758A (en) * | 2019-09-18 | 2019-12-20 | 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 |
| 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 |
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