CN102380353B - Method for preparing magnetic magnesium oxide surface molecular imprinting solid phase extractant - Google Patents
Method for preparing magnetic magnesium oxide surface molecular imprinting solid phase extractant Download PDFInfo
- Publication number
- CN102380353B CN102380353B CN 201110277240 CN201110277240A CN102380353B CN 102380353 B CN102380353 B CN 102380353B CN 201110277240 CN201110277240 CN 201110277240 CN 201110277240 A CN201110277240 A CN 201110277240A CN 102380353 B CN102380353 B CN 102380353B
- Authority
- CN
- China
- Prior art keywords
- magnetic oxygenated
- solid phase
- magnetic
- magnesium oxide
- oxygenated magnesium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Abstract
The invention relates to a method for preparing a magnetic magnesium oxide surface molecular imprinting solid phase extractant, which belongs to the technical field of environmental material preparation. The method comprises the following steps: preparing a magnetic magnesium oxide composite material by a coprecipitation method; then performing surface modification on the magnetic magnesium oxide composite material by cyclodextrin through a microemulsion method; finally preparing the surface molecular imprinting solid phase extractant based on the magnetic magnesium oxide composite material by suspension polymerization. A static state adsorption experiment is used for researching the adsorption balance, dynamics and selective recognition performance of the prepared imprinting adsorbent. The result shows that the magnetic magnesium oxide surface molecular imprinting solid phase extractant has high adsorption capacity, rapid absorption dynamic property and obvious thymol molecule recognition performance.
Description
Technical field
The present invention relates to a kind of method of utilizing the surface molecule print technology to prepare magnetic oxygenated magnesium solid extracting agent, belong to the environmentally conscious materials preparing technical field.
Background technology
Thymol extensive use in the production process of food additives, cosmetic essence, pharmaceutical intermediate and deodorant, but its excessive use meeting causes serious harm to environment and the mankind.Studies show that thymol can produce serious harm to the generation of human body cell plasma membrane and atriphos.Thymol in the therefore reasonable processing environment water sample is important link.At present solid phase extraction techniques extensive use study the technology of the wastewater treatment in environment.
Molecularly imprinted polymer is widely used in fields such as chromatographic isolation, biology sensor as a kind of novel solid extracting agent in recent years.Molecular imprinting is the covalently or non-covalently effect that utilizes between template molecule and the monomer, prepare by cross-linked polymeric and wash-out have specific structure, to the affine adsorptivity of template molecule and the technology of identifiability polymer.Embedding is dark excessively, wash-out is difficult, the shortcoming of poor selectivity yet traditional molecular imprinting has, so we have introduced the surface molecule print technology.The surface molecule print technology is by the molecular recognition site being based upon the surface of host material, improve recognition site and microsphere in conjunction with speed, further strengthen imprinted material adsorbing separation efficient.
For the ease of the separation of solid extracting agent, the magnetic metal oxide nano particle is desirable host material.Magnetic metal oxide nanoparticle surface trace adsorbent (MMIPs) utilizes the superparamagnetism of matrix and the specific adsorption effect of clad imprinted polymer, can be implemented in external magnetic field and assist to descend optionally target contaminant to be separated rapidly with mother liquor.We have prepared magnetic oxygenated magnesium base composite material by the method for co-precipitation, implement the trace polymerization on magnetic oxygenated magnesium base composite material surface subsequently, preferably resolve the problem that the magnetic metal oxide nano particle is reunited.The magnetic metal oxide nano particle is fixed on inorganic material surface or is coated on the peripheral preparation of inorganic material magnetic composite with macromolecular material, and the research at the surface imprinted modification acquisition of magnetic composite magnetic blotting polymeric adsorbant does not have report as yet again.
The present invention is function monomer with the cyclodextrin, combines with hydrogen bond and hydrophobic effect with template molecule, has reduced the combination of breaking ring function monomer and template molecule owing to solvent effect, also provides possibility for the water Synthesis of Molecular Imprinting Polymers simultaneously.
Summary of the invention
The present invention is means with the surface molecule print, prepares a kind of magnetic oxygenated magnesium solid extracting agent.Its advantage is effectively to have improved the trace hole with the intermolecular joint efficiency of template, has strengthened absorption property, has improved the selective of absorption.
The technical solution used in the present invention, a kind of preparation method of magnetic oxygenated magnesium surface molecule blotting solid phase extracter, carry out according to following step:
(1) preparation of magnetic oxygenated magnesium base composite material: the ferric trichloride and the magnesia that in flask, add mol ratio 2-4/0.5-1.0 (mmol:mmol), add distilled water and ultrasonic 0.5 hour according to distilled water and ferric trichloride with the ratio of 50-100/1 (mL/mmol) again, at room temperature stir after 1-2 hour and obtain stable suspension; Mol ratio according to ferric trichloride and frerrous chloride is to lead to nitrogen deoxygenation 10min after 2-4/0.5-1.0 (mmol/mmol) adds frerrous chloride then, stirs 0.5 hour with the speed continuation of 600rmp, is warming up to 70-80
oDropwise adding (5.0-10) mL/mmol mass concentration behind the C is 25% ammoniacal liquor, continues reaction and obtains the black product after 1-2 hour; Product separates by magnet, is washed till neutral back 60 with distilled water
oThe C vacuum drying; Prepare magnetic oxygenated magnesium base composite material;
(2) preparation of the magnetic oxygenated magnesium of cyclo-dextrin-modified: cyclodextrin is dissolved in N according to the concentration of 0.5-1/50-100 (mmol/mL), dinethylformamide, mol ratio according to cyclodextrin and sodium hydride is that 0.5-1/0.5-1 (mmol/mmol) adds sodium hydride then, and mixture at room temperature stirring reaction produces until no gas; Remove by filter excessive sodium hydride, in filtrate according to cyclodextrin and γ-(2,3-epoxy third oxygen) mol ratio of propyl trimethoxy silicane (KH-560) is that 0.5-1/1.0-2.0 (mmol/mmol) adds γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane (KH-560), after be warming up to 90
oC, reaction is 5 hours under nitrogen protection; The magnetic oxygenated magnesium base composite material mol ratio that makes according to cyclodextrin and step (1) in mixed liquor is that 0.5-1/1.0-2.0 (mmol/mmol) adds the magnetic oxygenated magnesium base composite material that step (1) makes then, and with above-mentioned substance volume and mol ratio be the N of 25-50 (mL/mmol), dinethylformamide, reaction temperature rises to 110-120
OCContinue reaction 24 hours.Product is used N respectively, and dinethylformamide, methyl alcohol and distilled water washing be back 60 for several times
oThe C vacuum drying;
(3) preparation of magnetic oxygenated magnesium surface molecularly imprinted polymer: thymol, methacrylic acid and dimethyl sulfoxide solution are mixed in the ratio of 1.0/3.0-4.0/10-20 (mmol/mmol/ml), to under dark shady and cool condition, leave standstill 12h behind the logical nitrogen purge oxygen of mixed liquor, form pre-assembling solution; In 1.0-1.5/1.5(g/ ml) ratio the magnetic oxygenated magnesium base composite material of the cyclo-dextrin-modified that makes in the step (2) is mixed with oleic acid stir 10min and form mixed solution, the ratio that adds 15-20 (mmol/mmol) glycol methacrylate again in every mM thymol, the pre-assembling solution that in above-mentioned mixed solution, adds crosslinking agent (glycol methacrylate) and make, under 300-400rpm, stir 30min, form pre-polymer solution.Ratio in every mM thymol adding 0.2-0.4 (g/mmol) polyvinylpyrrolidone adds dispersant in pre-polymer solution subsequently, add 100-120 (mmol/mL) methyl-sulfoxide and water mixed liquid (9:1, ratio adding solvent V/V) by every mM thymol at last.Lead to nitrogen purge oxygen stir 30min under 300-400rpm after, the ratio in every mM thymol adding 0.2-0.4 (g/mmol) azo-bis-isobutyl cyanide adds initator in reaction system.Be reflected under the nitrogen protection 65-70 ℃ of reaction 18-24h.The magnetic oxygenated magnesium base composite material surface print solid-phase extractant of product is collected with the Nd-Fe-B permanent magnet, washs 3 times with absolute ethyl alcohol and distilled water.(95:5 is the cable-styled extraction of extract 48h V/V) to the mixed liquor of end product usefulness methyl alcohol and acetic acid, removes template molecule, 60 ℃ of following vacuum drying.
Technological merit of the present invention: formed the trace hole by the surface molecule print technology on the host material surface, avoided because embedding is crossed dark and the wash-out difficulty; It is big that the magnetic oxygenated magnesium solid extracting agent for preparing has adsorption capacity, quick adsorption dynamics adsorption kinetics, and what specific adsorption was good has a few.
Description of drawings
The XRD diagram of the magnetic oxygenated magnesium base composite material of Fig. 1 and magnetic molecularly imprinted polymer can be observed Fe from Fig. 1
3O
4Characteristic peak in 2 θ=30.2 °, 35.6 °, 43.3 °, 53.5 °, locate the same Fe of magnetic oxygenated magnesium surface molecule blotting solid phase extracter for 57.2 ° and 62.8 °
3O
4Crystal formation similar;
The SEM diagram of Fig. 2 magnetic molecularly imprinted polymer and non-imprinted polymer, magnetic oxygenated magnesium surface molecule blotting solid phase extracter surface is owing to existing the trace hole to present irregular rough morphology; But not imprinted polymer surface smoother then;
The FT-IR diagram of the magnetic oxygenated magnesium base composite material of Fig. 3 and magnetic molecularly imprinted polymer, the surperficial cyclo-dextrin-modified of magnetic oxygenated magnesium and surface imprinted process have successfully been carried out as seen from the figure;
The TGA diagram of the magnetic oxygenated magnesium base composite material of Fig. 4 and magnetic molecularly imprinted polymer, magnetic oxygenated magnesium base composite material and magnetic molecularly imprinted polymer are 200 ℃ of following better heat stability as seen from the figure;
The VSM diagram of the magnetic oxygenated magnesium base composite material of Fig. 5 and magnetic molecularly imprinted polymer, the saturation magnetization of magnetic oxygenated magnesium base composite material and magnetic molecularly imprinted polymer is respectively 10.0emu/g and 4.79emu/g as seen from the figure, and the separating effect of magnetic molecularly imprinted polymer under externally-applied magnetic field is remarkable.
The specific embodiment
The evaluation of absorption property is undertaken by Staticadsorption experiment, will be statically placed in thermostat water bath behind the 10mL thymol solution adding colorimetric cylinder.Investigate time of repose, temperature and analogue and disturbed the influence of the trace adsorbent being identified the thymol molecule.After the absorption, test fluid at the middle and upper levels clear liquid with Nd-Fe-B permanent magnet separated and collected, Xi Fu thymol molecular concentration high-performance liquid chromatogram determination not, and according to the result calculate adsorption capacity (
Q e, mg/g).
C wherein
0(mg/L) and C
e(mg/L) be respectively the concentration of thymol before and after the absorption, W (g) is the adsorbent consumption, and V (mL) is the test fluid volume.
Corresponding non-trace adsorbent preparation method is similar, but does not add thymol.
The present invention will be further described below in conjunction with concrete embodiment.
Embodiment 1:(1) preparation of magnetic oxygenated magnesium: in the flask of 250mL, added behind 2.36 g ferric trichlorides, 1.0g magnesia and the 50mL distilled water ultrasonic 30 minutes, and at room temperature stirred after 3 hours and obtain stable suspension; Stirred 30 minutes with the speed continuation of 800rmp after adding the nitrogen deoxygenation of 0.86g protochloride Tie Tong then, be warming up to 80
oThe ammoniacal liquor that dropwise adds 5.0mL 25% behind the C continues reaction and obtains the black product after 1 hour; Product is washed till neutral back 60 with distilled water
oThe C vacuum drying.
(2) preparation of the magnetic oxygenated magnesium of cyclo-dextrin-modified: the 1.19g cyclodextrin is dissolved in 50mL N, adds 0.25g NaH behind the dinethylformamide again, mixed liquor at room temperature produces until no gas with the 300rpm stirring reaction; After removing by filter excessive sodium hydride filtrate is transferred to the 250mL flask, letting nitrogen in and deoxidizing 10min behind the adding 1.0g KH-560 is warming up to 90
o C reaction 5 hours; Add magnetic oxygenated magnesium, 25mL N that 1.25g prepares then, dinethylformamide is warming up to 110-120
OCReacted 24 hours; Product is used N respectively, and dinethylformamide, methyl alcohol and distilled water washing be back 60 for several times
oThe C vacuum drying;
(3) preparation of magnetic oxygenated magnesium surface molecularly imprinted polymer: 1.0mmol thymol and 3.0mmol methacrylic acid are joined in the 10ml dimethyl sulfoxide solution, to under dark shady and cool condition, leave standstill 12h behind the logical nitrogen purge oxygen of mixed liquor, form pre-assembling solution.Take by weighing the magnetic oxygenated magnesium base composite material of cyclo-dextrin-modified that 1.0g makes and join in the 1.0ml oleic acid and stir 10min, add pre-assembling solution and 15mL glycol methacrylate, under 300rpm, stir 30min, form pre-polymer solution.Add subsequently 0.2g polyvinylpyrrolidone and 80ml methyl-sulfoxide and water mixed liquor (9:1, V/V).Stir 30min under 300-400rpm after, logical nitrogen purge oxygen adds the 0.2g azodiisobutyronitrile.60 ℃ of reaction 24h under nitrogen protection.The magnetic oxygenated magnesium surface print solid-phase extractant of product is collected with the Nd-Fe-B permanent magnet, washs 3 times with absolute ethyl alcohol and distilled water.(95:5 is the cable-styled extraction of extract 48h V/V) to the mixed liquor of end product usefulness methyl alcohol and acetic acid, removes template molecule, 60 ℃ of following vacuum drying.Corresponding non-trace adsorbent preparation method is similar, but does not add thymol.
Embodiment 2:(1) preparation of magnetic oxygenated magnesium: in the flask of 250mL, added behind 4.72 g ferric trichlorides, 2.0g magnesia and the 180mL distilled water ultrasonic 30 minutes, and at room temperature stirred after 3 hours and obtain stable suspension; Stirred 30 minutes with the speed continuation of 800rmp after adding the nitrogen deoxygenation of 1.72g protochloride Tie Tong then, be warming up to 80
oThe ammoniacal liquor that dropwise adds 10mL 25% behind the C continues reaction and obtains the black product after 1 hour; Product is washed till neutral back 60 with distilled water
oThe C vacuum drying.
(2) preparation of the magnetic oxygenated magnesium of cyclo-dextrin-modified: the 2.29g cyclodextrin is dissolved in 100mL N, adds 0.5g NaH behind the dinethylformamide again, mixed liquor at room temperature produces until no gas with the 300rpm stirring reaction; After removing by filter excessive sodium hydride filtrate is transferred to the 250mL flask, letting nitrogen in and deoxidizing 10min behind the adding 2.0g KH-560 is warming up to 90
o C reaction 5 hours; Add magnetic oxygenated magnesium, 50mL N that 2.5g prepares then, dinethylformamide is warming up to 110-120
OCReacted 24 hours; Product is used N respectively, and dinethylformamide, methyl alcohol and distilled water washing be back 60 for several times
oThe C vacuum drying;
(3) preparation of magnetic oxygenated magnesium surface molecularly imprinted polymer: 1.0mmol thymol and 4.0mmol methacrylic acid are joined in the 10ml dimethyl sulfoxide solution, to under dark shady and cool condition, leave standstill 12h behind the logical nitrogen purge oxygen of mixed liquor, form pre-assembling solution.Take by weighing the magnetic oxygenated magnesium base composite material of cyclo-dextrin-modified that 1.5g makes and join in the 1.0ml oleic acid and stir 10min, add pre-assembling solution and 20ml glycol methacrylate, under 300rpm, stir 30min, form pre-polymer solution.Add subsequently 0.45g polyvinylpyrrolidone and 120ml methyl-sulfoxide and water mixed liquor (9:1, V/V).Stir 30min under 300-400rpm after, logical nitrogen purge oxygen adds 0.4gAIBN.60 ℃ of reaction 24h under nitrogen protection.The magnetic oxygenated magnesium surface print solid-phase extractant of product is collected with the Nd-Fe-B permanent magnet, washs 3 times with absolute ethyl alcohol and distilled water.(95:5 is the cable-styled extraction of extract 48h V/V) to the mixed liquor of end product usefulness methyl alcohol and acetic acid, removes template molecule, 60 ℃ of following vacuum drying.Corresponding non-trace adsorbent preparation method is similar, but does not add thymol.
Test example 1: get the 10ml initial concentration be respectively 20,40,60,80,100,150,200,250,300,400 and the thymol solution of 500mg/l join in the colorimetric cylinder, regulating the pH value with watery hydrochloric acid or weak aqua ammonia is 7.0, add 10mg trace and non-trace adsorbent respectively, test fluid is placed on leave standstill 12h in 25 ℃ the water-bath after, supernatant liquor Nd-Fe-B permanent magnet separated and collected, Xi Fu thymol molecular concentration high-performance liquid chromatogram determination not, and calculate adsorption capacity according to the result.The result shows that the saturated adsorption capacity of magnetic oxygenated magnesium surface molecule blotting solid phase extracter is 140.3mg/g.
Test example 2: getting the 10ml initial concentration is that 100mg/l thymol solution joins in the colorimetric cylinder, regulating the pH value with watery hydrochloric acid or weak aqua ammonia is 7.0, add 10mg trace and non-trace adsorbent respectively, test fluid is placed on leaves standstill 5,15,30,60,120,180,240 and 360min in 25 ℃ the water-bath respectively.After time of repose was finished, supernatant liquor was with Nd-Fe-B permanent magnet separated and collected, Xi Fu thymol molecular concentration high-performance liquid chromatogram determination not, and calculate adsorption capacity according to the result.The result shows, compares with non-trace adsorbent, and magnetic oxygenated magnesium surface molecule blotting solid phase extracter has higher adsorption capacity and adsorption dynamics adsorption kinetics performance faster to the thymol molecule.
Test example 3: the similar two kinds of phenol sesamols of choice structure and 2-isopropyl-phenol are the phenol of competitive Adsorption, the configuration thymol, and the mixed solution of sesamol and 2-isopropyl-phenol, the concentration of every kind of phenol all is 100mg/l.Get the mixed solution that 10ml configures and join in the colorimetric cylinder, regulating the pH value with watery hydrochloric acid or weak aqua ammonia is 7.0, adds 10mg trace and non-trace adsorbent respectively, test fluid is placed in 25 ℃ the water-bath and leaves standstill 12.0h respectively.After time of repose was finished, supernatant liquor was with Nd-Fe-B permanent magnet separated and collected, Xi Fu three kinds of phenol concentration high-performance liquid chromatogram determinations not, according to following formula calculate distribution coefficient (
K d), selectivity factor (
k) and the relative selectivity coefficient (
K ').
Wherein
XBe the phenol of competitive Adsorption,
k MWith
k NIt is respectively the selectivity factor of trace adsorbent and non-trace adsorbent.Experimental result sees Table 1, and the result shows, magnetic molecularly imprinted polymer is 18.6 times of sesamol to the adsorptive selectivity of thymol, is 4.57 times of 2-isopropyl-phenol, and recognition performance is remarkable.
The adsorptive selectivity contrast of table 1 magnetic molecularly imprinted polymer and non-imprinted polymer
Claims (1)
1. the preparation method of a magnetic oxygenated magnesium surface molecule blotting solid phase extracter is characterized in that carrying out according to following step:
(1) preparation of magnetic oxygenated magnesium: in the flask of 250mL, added behind 2.36 g ferric trichlorides, 1.0g magnesia and the 50mL distilled water ultrasonic 30 minutes, and at room temperature stirred after 3 hours and obtain stable suspension; Stirred 30 minutes with the speed continuation of 800rpm after adding the nitrogen deoxygenation of 0.86g protochloride Tie Tong then, be warming up to the ammoniacal liquor that dropwise adds 5.0mL 25% after 80 ℃, continue reaction and obtaining the black product after 1 hour; Product is washed till neutral back 60 ℃ of vacuum drying with distilled water;
(2) preparation of the magnetic oxygenated magnesium of cyclo-dextrin-modified: the 1.19g cyclodextrin is dissolved in 50mL N, adds 0.25g NaH behind the dinethylformamide again, mixed liquor at room temperature produces until no gas with the 300rpm stirring reaction; After removing by filter excessive sodium hydride filtrate is transferred to the 250mL flask, letting nitrogen in and deoxidizing 10min behind the adding 1.0g KH-560 is warming up to 90 ℃ of reactions 5 hours; Add magnetic oxygenated magnesium, 25mL N that 1.25g prepares then, dinethylformamide is warming up to 110-120 ℃ of reaction 24 hours; Product is used N respectively, dinethylformamide, methyl alcohol and distilled water washing back 60 ℃ of vacuum drying for several times;
(3) preparation of magnetic oxygenated magnesium surface molecule blotting solid phase extracter: 1.0mmol thymol and 3.0mmol methacrylic acid are joined in the 10mL dimethyl sulfoxide solution; to under dark shady and cool condition, leave standstill 12h behind the logical nitrogen purge oxygen of mixed liquor; form pre-assembling solution; taking by weighing the magnetic oxygenated magnesium of cyclo-dextrin-modified that 1.0g makes joins in the 1.0mL oleic acid and stirs 10min; add pre-assembling solution and 15mL glycol methacrylate; under 300rpm, stir 30min; form pre-polymer solution; adding 0.2g polyvinylpyrrolidone and methyl-sulfoxide and water volume ratio subsequently is the mixed liquor 80mL of 9:1; after under 300-400rpm, stirring 30min; logical nitrogen purge oxygen; add the 0.2g azodiisobutyronitrile; 60 ℃ of reaction 24h under nitrogen protection; magnetic oxygenated magnesium surface molecule blotting solid phase extracter is collected with the Nd-Fe-B permanent magnet; wash 3 times with absolute ethyl alcohol and distilled water; end product is that the mixed liquor of 95:5 is the cable-styled extraction of extract 48h with methyl alcohol and acetic acid volume ratio; remove template molecule, 60 ℃ of following vacuum drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110277240 CN102380353B (en) | 2011-09-19 | 2011-09-19 | Method for preparing magnetic magnesium oxide surface molecular imprinting solid phase extractant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110277240 CN102380353B (en) | 2011-09-19 | 2011-09-19 | Method for preparing magnetic magnesium oxide surface molecular imprinting solid phase extractant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102380353A CN102380353A (en) | 2012-03-21 |
| CN102380353B true CN102380353B (en) | 2013-08-21 |
Family
ID=45820427
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110277240 Expired - Fee Related CN102380353B (en) | 2011-09-19 | 2011-09-19 | Method for preparing magnetic magnesium oxide surface molecular imprinting solid phase extractant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102380353B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102784626A (en) * | 2012-08-08 | 2012-11-21 | 江苏大学 | Temperature-sensitive magnetic sulfadimidine molecular imprinted adsorbent as well as preparation method and application thereof |
| CN109331795A (en) * | 2018-10-31 | 2019-02-15 | 沈阳药科大学 | A kind of magnetic nanometer composite material and its preparation and application |
| CN109734929B (en) * | 2019-01-07 | 2021-07-13 | 安徽中烟工业有限责任公司 | Preparation method and application of maltol magnetic molecularly imprinted solid-phase extraction material with core-shell microsphere structure |
| CN110961086B (en) * | 2019-12-15 | 2021-12-03 | 江西理工大学 | Extractant functionalized magnetic nano-adsorption material, preparation method and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101516448A (en) * | 2006-09-19 | 2009-08-26 | 巴斯夫欧洲公司 | Cosmetic preparations based on molecularly imprinted polymers |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6844289B2 (en) * | 2003-04-08 | 2005-01-18 | Invista North America S.A.R.L. | Process for the preparation of a nickel/phosphorous ligand catalyst |
| JP4367126B2 (en) * | 2003-12-19 | 2009-11-18 | 和光純薬工業株式会社 | Measuring method |
| WO2010018418A1 (en) * | 2008-08-12 | 2010-02-18 | Novatech D.O.O. | Formulation based on micronized clinoptilolite as therapeutic agent providing highly bioavailable silicon |
-
2011
- 2011-09-19 CN CN 201110277240 patent/CN102380353B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101516448A (en) * | 2006-09-19 | 2009-08-26 | 巴斯夫欧洲公司 | Cosmetic preparations based on molecularly imprinted polymers |
Non-Patent Citations (1)
| Title |
|---|
| JP特开2005-181106A 2005.07.07 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102380353A (en) | 2012-03-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Shao et al. | Magnetic responsive metal–organic frameworks nanosphere with core–shell structure for highly efficient removal of methylene blue | |
| Shao et al. | Preparation of novel magnetic molecular imprinted polymers nanospheres via reversible addition–fragmentation chain transfer polymerization for selective and efficient determination of tetrabromobisphenol A | |
| CN102898566B (en) | Preparation method of metal organic framework molecularly imprinted polymer used for enriching trace amounts of Metolcarb | |
| Sheng et al. | Well-defined magnetic surface imprinted nanoparticles for selective enrichment of 2, 4-dichlorophenoxyacetic acid in real samples | |
| CN102532408B (en) | Preparation method of temperature sensitive magnetic western-blotting nanosphere | |
| CN102380353B (en) | Method for preparing magnetic magnesium oxide surface molecular imprinting solid phase extractant | |
| CN103506093A (en) | Magnetic dual-template protein molecule imprinted nano particle and preparation method thereof | |
| CN106483218B (en) | A kind of molecular engram solid phase extraction-liquid chromatogram detects metrifonate and Azodrin method simultaneously | |
| CN107129562B (en) | Magnetic nanocrystalline cellulose grafted graphene oxide surface molecularly imprinted polymer | |
| CN102702429A (en) | Method for preparing bisphenol A molecularly imprinted polymer | |
| CN106046256B (en) | The preparation method of geniposide molecular engram polymer magnetic microballoon | |
| Cui et al. | Facile construction of magnetic hydrophilic molecularly imprinted polymers with enhanced selectivity based on dynamic non-covalent bonds for detecting tetracycline | |
| CN103897123A (en) | Method for preparing nuclear-shell type magnetic composite microsphere with surface rich in nickel ions and application of nuclear-shell type magnetic composite microsphere | |
| CN109647364A (en) | A kind of preparation method of the recyclable magnetic adsorptive material for heavy metal processing | |
| CN102489273B (en) | Preparation method of magnetic beads of dendritic molecular imprinting polymer on surface of estrogenic nano silica gel | |
| Zhao et al. | Facile fabrication of surface molecularly imprinted magnetic polydopamine for selective adsorption of fluoroquinolone from aqueous solutions | |
| Bakhshpour et al. | Affinity binding of proteins to the modified bacterial cellulose nanofibers | |
| CN103599757B (en) | The preparation method of a kind of magnetic temp-sensitive type surface strontium ion trace adsorbent | |
| Lan et al. | Study on the polypeptide-functionalized magnetic chitosan microspheres that specifically adsorb Hg (II) ions | |
| Zhu et al. | Dual-responsive copolymer hydrogel as broad-spectrum adsorbents for metal ions | |
| Altıntaş et al. | Monosize magnetic hydrophobic beads for lysozyme purification under magnetic field | |
| CN103613722A (en) | Method for preparing magnetic halloysite molecularly imprinted polymer with specific adsorption to 2,4-dichlorophenoxyacetic acid | |
| CN112979893A (en) | Preparation of magnetic fluorescent material @ molecularly imprinted particle and method for preparing composite membrane by using same | |
| CN115920864B (en) | Magnetic amino functional core-shell composite material and preparation method thereof | |
| CN108854154B (en) | Peanut shell polyphenol selective enrichment method using magnetic microspheres |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: ZHENJIANG GAOPENG MEDICINE CO., LTD. Free format text: FORMER OWNER: JIANGSU UNIVERSITY Effective date: 20140108 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 212013 ZHENJIANG, JIANGSU PROVINCE TO: 212006 ZHENJIANG, JIANGSU PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20140108 Address after: 212006 No. 51 Linjiang West Road, New District, Jiangsu, Zhenjiang Patentee after: Zhenjiang Gaopeng Pharmaceutical Co., Ltd. Address before: Zhenjiang City, Jiangsu Province, 212013 Jingkou District Road No. 301 Patentee before: Jiangsu University |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130821 Termination date: 20180919 |