CN102380353A - 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
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- CN102380353A CN102380353A CN2011102772402A CN201110277240A CN102380353A CN 102380353 A CN102380353 A CN 102380353A CN 2011102772402 A CN2011102772402 A CN 2011102772402A CN 201110277240 A CN201110277240 A CN 201110277240A CN 102380353 A CN102380353 A CN 102380353A
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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 magnetic oxygenated magnesium solid extracting agent of surface molecule print technology preparation, 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 the environment and the mankind.Research shows 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 new solid-state extractant in recent years.Molecular imprinting is the covalently or non-covalently effect that utilizes between template molecule and the monomer, prepare through 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 through being based upon the molecular recognition site on the surface of host material, improves the speed that combines of recognition site and microsphere, further strengthens 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 through 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 owing to solvent effect is broken combining of ring function monomer and template molecule, also provides possible 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 selectivity of absorption.
The technical scheme that the present invention adopts, 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 through 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 filtrating 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 in mixed liquor, makes according to cyclodextrin and step (1) then is that 0.5-1/1.0-2.0 (mmol/mmol) adds the magnetic oxygenated magnesium base composite material that step (1) makes; 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: the mixed of thymol, methacrylic acid and dimethyl sulfoxide solution being pressed 1.0/3.0-4.0/10-20 (mmol/mmol/ml); With under dark shady and cool condition, leaving standstill 12h behind the logical nitrogen purge oxygen of mixed liquor, form preparatory assembled solution; In the ratio of 1.0-1.5/1.5 (g/ ml) the magnetic oxygenated magnesium base composite material of the cyclo-dextrin-modified that makes in the step (2) is mixed with oleic acid and to stir 10min and form mixed solution; The ratio that adds 15-20 (mmol/mmol) glycol methacrylate again in every mM thymol; The preparatory assembled 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 after under 300-400rpm, stirring 30min, 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 end product, removes template molecule, 60 ℃ of following vacuum drying with the mixed liquor of methyl alcohol and acetic acid.
Technological merit of the present invention: formed the trace hole through the surface molecule print technology on the host material surface, avoided that wash-out is difficult because embedding is crossed dark; 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 figure of magnetic oxygenated magnesium base composite material of Fig. 1 and magnetic molecularly imprinted polymer shows, 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 of magnetic oxygenated magnesium base composite material of Fig. 3 and magnetic molecularly imprinted polymer diagram can know that by figure the surperficial cyclo-dextrin-modified of magnetic oxygenated magnesium and surface imprinted process successfully carried out;
The TGA diagram of magnetic oxygenated magnesium base composite material of Fig. 4 and magnetic molecularly imprinted polymer can know that by figure magnetic oxygenated magnesium base composite material and magnetic molecularly imprinted polymer are 200 ℃ of following better heat stability;
The VSM diagram of magnetic oxygenated magnesium base composite material of Fig. 5 and magnetic molecularly imprinted polymer; Can know that by figure the saturation magnetization of magnetic oxygenated magnesium base composite material and magnetic molecularly imprinted polymer is respectively 10.0emu/g and 4.79emu/g, the separating effect of magnetic molecularly imprinted polymer under externally-applied magnetic field is remarkable.
The specific embodiment
The evaluation of absorption property is carried out through Staticadsorption experiment, with being statically placed in thermostat water bath behind the 10mL thymol solution adding colorimetric cylinder.Investigated time of repose, temperature and analogue and disturbed influence trace adsorbent identification thymol molecule.After the absorption, test fluid at the middle and upper levels clear liquid with Nd-Fe-B permanent magnet separated and collected, absorption the thymol molecular concentration do not use high-performance liquid chromatogram determination, 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.
Below in conjunction with the practical implementation instance the present invention is further specified.
Embodiment 1: the preparation of (1) 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 filtrating is transferred to the 250mL flask, letting nitrogen in and deoxidizing 10min behind the adding 1.0g KH-560 is warming up to 90
oC 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; With under dark shady and cool condition, leaving standstill 12h behind the logical nitrogen purge oxygen of mixed liquor, form preparatory assembled 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 preparatory assembled 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).After under 300-400rpm, stirring 30min, 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 end product, removes template molecule, 60 ℃ of following vacuum drying with the mixed liquor of methyl alcohol and acetic acid.Corresponding non-trace adsorbent preparation method is similar, but does not add thymol.
Embodiment 2: the preparation of (1) 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 filtrating is transferred to the 250mL flask, letting nitrogen in and deoxidizing 10min behind the adding 2.0g KH-560 is warming up to 90
oC 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; With under dark shady and cool condition, leaving standstill 12h behind the logical nitrogen purge oxygen of mixed liquor, form preparatory assembled 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 preparatory assembled 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).After under 300-400rpm, stirring 30min, 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 end product, removes template molecule, 60 ℃ of following vacuum drying with the mixed liquor of methyl alcohol and acetic acid.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; Using watery hydrochloric acid or weak aqua ammonia to regulate the pH value is 7.0; Add 10mg trace and non-trace adsorbent respectively; Be placed on test fluid leave standstill 12h in 25 ℃ the water-bath after; Supernatant liquor is with Nd-Fe-B permanent magnet separated and collected, and the thymol molecular concentration of absorption is not used high-performance liquid chromatogram determination, and calculates 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; Using watery hydrochloric acid or weak aqua ammonia to regulate the pH value is 7.0; Add 10mg trace and non-trace adsorbent respectively, be placed on test fluid and leave standstill 5,15,30,60,120,180,240 and 360min in 25 ℃ the water-bath respectively.After time of repose was accomplished, supernatant liquor was with Nd-Fe-B permanent magnet separated and collected, and the thymol molecular concentration of absorption is not used high-performance liquid chromatogram determination, and calculates 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: 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, using watery hydrochloric acid or weak aqua ammonia to regulate the pH value is 7.0, adds 10mg trace and non-trace adsorbent respectively, is placed on test fluid in 25 ℃ the water-bath and leaves standstill 12.0h respectively.After time of repose was accomplished, supernatant liquor was with Nd-Fe-B permanent magnet separated and collected, and three kinds of phenol concentration of adsorbing are not used high-performance liquid chromatogram determination, 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 is seen 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 base composite material: the ferric trichloride and the magnesia that in flask, add mol ratio 2-4/0.5-1.0; Add distilled water and ultrasonic 0.5 hour according to distilled water and ferric trichloride with the ratio of 50-100/1 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 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 behind the C) mL/mmol mass concentration is 25% ammoniacal liquor, continues reaction and obtaining the black product after 1-2 hour; Product separates through 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; Dinethylformamide; Mol ratio according to cyclodextrin and sodium hydride is that 0.5-1/0.5-1 adds sodium hydride then, and mixture at room temperature stirring reaction produces until no gas; Removing by filter excessive sodium hydride, is that 0.5-1/1.0-2.0 adds γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane according to the mol ratio of cyclodextrin and γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane in filtrating, after be warming up to 90
oC, reaction is 5 hours under nitrogen protection; The magnetic oxygenated magnesium base composite material mol ratio that in mixed liquor, makes according to cyclodextrin and step (1) then is that 0.5-1/1.0-2.0 adds the magnetic oxygenated magnesium base composite material that step (1) makes; And with above-mentioned substance volume and mol ratio be the N of 25-50; 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: the mixed of thymol, methacrylic acid and dimethyl sulfoxide solution being pressed 1.0/3.0-4.0/10-20; With under dark shady and cool condition, leaving standstill 12h behind the logical nitrogen purge oxygen of mixed liquor, form preparatory assembled solution; In the ratio of 1.0-1.5/1.5 the magnetic oxygenated magnesium base composite material of the cyclo-dextrin-modified that makes in the step (2) is mixed with oleic acid and to stir 10min and form mixed solution; The ratio that adds the 15-20 glycol methacrylate again in every mM thymol; In above-mentioned mixed solution, add crosslinking agent glycol methacrylate and the preparatory assembled solution that makes; Under 300-400rpm, stir 30min, form pre-polymer solution; Ratio in every mM thymol adding 0.2-0.4 polyvinylpyrrolidone adds dispersant in pre-polymer solution subsequently, adds 100-120 methyl-sulfoxide and water mixed liquid (9:1, ratio adding solvent V/V) by every mM thymol at last; Lead to nitrogen purge oxygen after under 300-400rpm, stirring 30min, the ratio in every mM thymol adding 0.2-0.4 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; End product uses the mixed liquor of volume ratio 95:5 methyl alcohol and acetic acid as the cable-styled extraction of extract 48h, removes template molecule, 60 ℃ of following vacuum drying.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN109734929A (en) * | 2019-01-07 | 2019-05-10 | 安徽中烟工业有限责任公司 | A kind of preparation method and applications of the magnetic molecularly imprinted solid phase extraction material of maltol of core-shell particles structure |
| CN110961086A (en) * | 2019-12-15 | 2020-04-07 | 江西理工大学 | Extractant functionalized magnetic nano-adsorption material, preparation method and application |
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| JP2005181106A (en) * | 2003-12-19 | 2005-07-07 | Wako Pure Chem Ind Ltd | Measuring method |
| CN101516448A (en) * | 2006-09-19 | 2009-08-26 | 巴斯夫欧洲公司 | Cosmetic preparations based on molecularly imprinted polymers |
| WO2010018418A1 (en) * | 2008-08-12 | 2010-02-18 | Novatech D.O.O. | Formulation based on micronized clinoptilolite as therapeutic agent providing highly bioavailable silicon |
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| US20040204312A1 (en) * | 2003-04-08 | 2004-10-14 | Jackson Scott Christopher | Process for the preparation of a nickel/phosphorous ligand catalyst |
| JP2005181106A (en) * | 2003-12-19 | 2005-07-07 | Wako Pure Chem Ind Ltd | Measuring method |
| CN101516448A (en) * | 2006-09-19 | 2009-08-26 | 巴斯夫欧洲公司 | Cosmetic preparations based on molecularly imprinted polymers |
| WO2010018418A1 (en) * | 2008-08-12 | 2010-02-18 | Novatech D.O.O. | Formulation based on micronized clinoptilolite as therapeutic agent providing highly bioavailable silicon |
Cited By (6)
| 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 |
| CN109734929A (en) * | 2019-01-07 | 2019-05-10 | 安徽中烟工业有限责任公司 | A kind of preparation method and applications of the magnetic molecularly imprinted solid phase extraction material of maltol of core-shell particles structure |
| 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 |
| CN110961086A (en) * | 2019-12-15 | 2020-04-07 | 江西理工大学 | Extractant functionalized magnetic nano-adsorption material, preparation method and application |
| CN110961086B (en) * | 2019-12-15 | 2021-12-03 | 江西理工大学 | Extractant functionalized magnetic nano-adsorption material, preparation method and application |
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Owner name: ZHENJIANG GAOPENG MEDICINE CO., LTD. Free format text: FORMER OWNER: JIANGSU UNIVERSITY Effective date: 20140108 |
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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 |
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