CN108452781A - The preparation method of core-shell magnetic gamma-cyclodextrin polymer composites and application - Google Patents
The preparation method of core-shell magnetic gamma-cyclodextrin polymer composites and application Download PDFInfo
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- CN108452781A CN108452781A CN201810282059.2A CN201810282059A CN108452781A CN 108452781 A CN108452781 A CN 108452781A CN 201810282059 A CN201810282059 A CN 201810282059A CN 108452781 A CN108452781 A CN 108452781A
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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Abstract
The invention discloses a kind of preparation method of core-shell magnetic γ cyclodextrin composite materials and applications.The composite material is by poly-dopamine（PDA）And cyclodextrin（P‑CDP）It coats layer by layer；Wherein, about 20 nm of P CDP layer thickness.The composite material of gained of the invention, in heating water bath under lasting stirring condition, can realize uniform cladding of the cyclodextrin on magnetic ball using PDA as adhesive.Compared with simple cyclodextrin polymer material, composite material has had both magnetic property so that separation of solid and liquid is simpler rapid, while the uniform cladding of cyclodextrin makes have more adsorption site on composite material.Preparation process of the present invention is simple, and gained composite material has good separation and concentration effect to Microcystin, has good application prospect in the fields such as Analysis of water environment and culture fishery Risk-warning.
Description
Technical field
The invention belongs to the preparing technical fields of sorbing material, and in particular to a kind of core-shell magnetic gamma-cyclodextrin polymer
The preparation method of composite material and application.
Background technology
Solid Phase Extraction（Solid-phase extraction, SPE）It is the common pre-treatment side of algae toxin separation and concentration
Method.SPE has many advantages, such as that easy to operate, solvent consumption is few.But there are also well-known disadvantages by SPE.For example, extraction
The easy blocking of pillar, operating process is taken to take longer etc..In order to overcome these disadvantages, and the new skill of some Solid Phase Extraction is derived
Art new method, such as Magnetic solid phases extraction（Magnetic solid-phase extraction, MSPE）, it passes through permanent magnet
The help of the externally-applied magnetic field of generation so that the separation of the solid-phase adsorbent and sample solution of magnetization becomes simpler.Currently,
Bonded silica gel particle, carbon-rich material, molecularly imprinted polymer, the materials such as metal-organic framework materials are commonly used for the absorption of MSPE
Agent.
Cyclodextrin（CD）It is a kind of cyclic oligosaccharide formed by several glucose monomers, possesses hydrophobic cavity and parent
Aqueous outer surface.This special cavity structure makes CD that can be used as a kind of host molecule in main-guest chemistry research,
Can the various organic guest molecules of selective binding enter its hydrophobic cavity in, formed Host-guest complex.Root
According to this characteristic, there is Host-guest interaction between the hydrophobic interior cavities of CD and the Adda hydrophobic groupings of Microcystin.In addition,
Water-soluble CD can be modified easily in macromolecule or solid matrix surface, and it is unique not only can to assign material
Host-guest interaction power, moreover it is possible to increase the aqueous phase dispersibility of functional material.Therefore, the functional composite material based on CD may
It is a kind of superior adsorbent extracting Microcystin in environmental water sample.
Invention content
It is an object of the invention in view of the shortcomings of the prior art, to provide a kind of core-shell magnetic gamma-cyclodextrin polymer compound
The preparation method of material and application.The composite material of gained of the invention is with poly-dopamine（PDA）For adhesive, heating water bath with
Continue under stirring condition, can realize uniform cladding of the cyclodextrin on magnetic ball.With simple cyclodextrin polymer material
It compares, composite material has had both magnetic property so that separation of solid and liquid is simpler rapid, while the uniform cladding of cyclodextrin
Make that there is more adsorption site on composite material.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of preparation method of core-shell magnetic gamma-cyclodextrin polymer composites, specifically includes following steps：
（One）Fe3O4The preparation of magnetic ball
（a）Weigh 4-8 g ferric chloride hexahydrates（FeCl3·6H2O）With 2-3 g trisodium citrates (Na3Cit·2H2O it) is dissolved in
150-300 mL ethylene glycol, obtains orange clear solution；
（b）Toward step（a）10-15 g sodium acetates are added in obtained solution（NaAc）, continue magnetic agitation to dissolving, gained is molten
Liquid is transferred in reaction kettle, is warming up to 200 DEG C of 12 h of sustained response；
（c）By step（b）Products therefrom is alternately washed with ultra-pure water and absolute ethyl alcohol, is dried after carrying out Magnetic Isolation with magnet
To Fe3O4Magnetic ball, it is spare；
（Two）Fe3O4The preparation of@PDA core-shell materials
（1）Weigh 0.1-0.2 g trishydroxymethylaminomethanes（Tris）It is dissolved in 80-150 mL secondary waters and is configured to 10 mM bufferings
Solution, with salt acid for adjusting pH to 8.5；
（2）Weigh 0.1-0.35 g steps（One）Fe obtained3O4Magnetic ball ultrasonic disperse is in step（1）The buffer solution of preparation
In, continuously add 0.2-0.4 g dopamines（DA）, 4 h of mechanical agitation at room temperature；
（3）After the completion of reaction, products therefrom ultra-pure water and absolute ethyl alcohol are alternately washed, dried after carrying out Magnetic Isolation with magnet
It is dry to obtain Fe3O4@PDA core-shell materials, it is spare；
（Three）The preparation of core-shell magnetic gamma-cyclodextrin polymer composites
（A）Weigh 1-2 g gamma-cyclodextrins（γ-CD）, 0.5-1 g tetrafluoros terephthalonitriles and 2-3 g potassium carbonate（K2CO3）In two
In neck round-bottom flask, 50-60 mL THF/DMF mixed solvents are added（THF:DMF=9:1 v/v）10 min of ultrasonic disperse；It is added
0.1-0.3 g steps（Two）Fe obtained3O4@PDA core-shell materials continue 10 min of ultrasonic disperse；
（B）By step（A）Gained reactant is heated to 85 DEG C, mechanical agitation and condensing reflux 2 days；
（C）After the completion of reaction, by products therefrom ultra-pure water, THF and dichloromethane（CH2Cl2）Magnet is used in supersound washing successively
Room temperature is dried after carrying out Magnetic Isolation, obtains the core-shell magnetic gamma-cyclodextrin polymer composites（Fe3O4@PDA@P-
CDP）.
Core-shell magnetic gamma-cyclodextrin polymer composites made from preparation method as described above, by poly-dopamine
（PDA）And cyclodextrin（P-CDP）It coats layer by layer；Wherein, cyclodextrin layer thickness is about 20 nm.
Core-shell magnetic gamma-cyclodextrin polymer composites can be used as Magnetic solid phases made from preparation method as described above
Adsorbent is extracted, in conjunction with liquid chromatograph-mass spectrometer（HPLC-MS）, it is applied to the extraction of Microcystin in water sample, specifically
Steps are as follows：
（i）Core-shell magnetic gamma-cyclodextrin polymer composites are added in the sample containing Microcystin, vortex is passed through
Or shaking mode promotes to adsorb, and with appropriate elution and eluent is collected after Magnetic Isolation, by supernatant and eluent
It is quantified with liquid chromatograph-mass spectrometer；
（ii）Under the chromatography of setting, mass spectrometry method, optimization eluent, adsorbent amount extraction time, elution time, absorption
pH；
（iii）Under conditions of optimal, the investigation of the range of linearity, detection line, sensitivity etc. is carried out to method；
（iiii）Detect the content of Microcystin in actual water sample.
The beneficial effects of the present invention are：
1）The method of the present invention design is simple, economical, the hydrophily of the core-shell magnetic gamma-cyclodextrin polymer composites of preparation
It is good, pore volume is big, Microcystin that can be in fast separating concentration water and there is good reproducibility and repeatability, for the material
The merchandized handling of material provides possibility；
2）The composite material of the present invention has good dispersibility in water, and its superparamagnetism is under external magnetic field
It can be achieved quickly to be separated by solid-liquid separation, can greatly shorten the operating time；
3）The present invention is sufficiently used the adhesion characteristics of poly-dopamine, improves cyclodextrin and coats unevenness on magnetic ball
Even situation, the hydrogen bond action of the hydroxyl on abundant catechol group and cyclodextrin, can be such that cyclodextrin shell coats thereon
More securely, this synthesis mode greatly be core-shell polymer synthesis provide convenience.
Description of the drawings
Fig. 1 is the transmission electron microscope picture of core-shell magnetic gamma-cyclodextrin polymer composites；
Fig. 2 is separation and concentration effect of the present invention gained core-shell magnetic gamma-cyclodextrin polymer composites to Microcystin
Figure.
Specific implementation mode
Below in conjunction with specific embodiment, the present invention will be further described, but the present invention is not limited only to these embodiments.
Embodiment 1
A kind of preparation method of core-shell magnetic gamma-cyclodextrin polymer composites, specifically includes following steps：
（One）Fe3O4The preparation of magnetic ball
（a）Weigh 6.8 g ferric chloride hexahydrates（FeCl3·6H2O）With 2.0 g trisodium citrates (Na3Cit·2H2O it) is dissolved in
200 mL ethylene glycol, obtain orange clear solution；
（b）Toward step（a）12.0 g sodium acetates are added in obtained solution（NaAc）, continue magnetic agitation to dissolving, gained is molten
Liquid is transferred in 80 mL reaction kettles, is warming up to 200 DEG C of 12 h of sustained response；
（c）By step（b）Products therefrom is alternately washed each 3 times, after carrying out Magnetic Isolation with magnet with ultra-pure water and absolute ethyl alcohol
Drying obtains Fe3O4Magnetic ball, it is spare；
（Two）Fe3O4The preparation of@PDA core-shell materials
（1）Weigh 0.121 g trishydroxymethylaminomethanes（Tris）It is dissolved in 100 mL secondary waters and is configured to 10 mM buffer solutions,
With salt acid for adjusting pH to 8.5；
（2）Weigh 0.2 g steps（One）Fe obtained3O4Magnetic ball ultrasonic disperse is in step（1）In the buffer solution of preparation, continue
0.4 g dopamines are added（DA）, 4 h of mechanical agitation at room temperature；
（3）After the completion of reaction, products therefrom ultra-pure water and absolute ethyl alcohol are alternately washed each 2 times, magnetic point is carried out with magnet
Fe is obtained from rear drying3O4@PDA core-shell materials, it is spare；
（Three）The preparation of core-shell magnetic gamma-cyclodextrin polymer composites
（A）Weigh 1.4 g gamma-cyclodextrins（γ-CD）, 0.7 g tetrafluoros terephthalonitrile and 2.1 g potassium carbonate（K2CO3）In two necks
In round-bottomed flask, 56 mL THF/DMF mixed solvents are added（THF:DMF=9:1 v/v）10 min of ultrasonic disperse；0.2 g is added
Step（Two）Fe obtained3O4@PDA core-shell materials continue 10 min of ultrasonic disperse；
（B）By step（A）Gained reactant is heated to 85 DEG C, mechanical agitation and condensing reflux 2 days；
（C）After the completion of reaction, by products therefrom ultra-pure water, THF and dichloromethane（CH2Cl2）Successively supersound washing 15,30,
15 min, room temperature is dried after carrying out Magnetic Isolation with magnet, obtains the core-shell magnetic gamma-cyclodextrin polymer composites
（Fe3O4@PDA@P-CDP）.
Embodiment 2
A kind of preparation method of core-shell magnetic gamma-cyclodextrin polymer composites, specifically includes following steps：
（One）Fe3O4The preparation of magnetic ball
（a）Weigh 4 g ferric chloride hexahydrates（FeCl3·6H2O）With 2 g trisodium citrates (Na3Cit·2H2O) it is dissolved in 150 mL
Ethylene glycol obtains orange clear solution；
（b）Toward step（a）10 g sodium acetates are added in obtained solution（NaAc）, continue magnetic agitation to dissolving, acquired solution
It is transferred in reaction kettle, is warming up to 200 DEG C of 12 h of sustained response；
（c）By step（b）Products therefrom is alternately washed each 3 times, after carrying out Magnetic Isolation with magnet with ultra-pure water and absolute ethyl alcohol
Drying obtains Fe3O4Magnetic ball, it is spare；
（Two）Fe3O4The preparation of@PDA core-shell materials
（1）Weigh 0.1 g trishydroxymethylaminomethanes（Tris）It is dissolved in 80 mL secondary waters and is configured to 10 mM buffer solutions, use salt
Acid for adjusting pH is to 8.5；
（2）Weigh 0.1 g steps（One）Fe obtained3O4Magnetic ball ultrasonic disperse is in step（1）In the buffer solution of preparation, continue
0.2 g dopamines are added（DA）, 4 h of mechanical agitation at room temperature；
（3）After the completion of reaction, products therefrom ultra-pure water and absolute ethyl alcohol are alternately washed each 2 times, magnetic point is carried out with magnet
Fe is obtained from rear drying3O4@PDA core-shell materials, it is spare；
（Three）The preparation of core-shell magnetic gamma-cyclodextrin polymer composites
（A）Weigh 1 g gamma-cyclodextrins（γ-CD）, 0.5 g tetrafluoros terephthalonitrile and 2 g potassium carbonate（K2CO3）In two neck round bottoms
In flask, 50 mL THF/DMF mixed solvents are added（THF:DMF=9:1 v/v）10 min of ultrasonic disperse；0.1 g steps are added
Suddenly（Two）Fe obtained3O4@PDA core-shell materials continue 10 min of ultrasonic disperse；
（B）By step（A）Gained reactant is heated to 85 DEG C, mechanical agitation and condensing reflux 2 days；
（C）After the completion of reaction, by products therefrom ultra-pure water, THF and dichloromethane（CH2Cl2）Successively supersound washing 15,30,
15 min, room temperature is dried after carrying out Magnetic Isolation with magnet, obtains the core-shell magnetic gamma-cyclodextrin polymer composites
（Fe3O4@PDA@P-CDP）.
Embodiment 3
A kind of preparation method of core-shell magnetic gamma-cyclodextrin polymer composites, specifically includes following steps：
（One）Fe3O4The preparation of magnetic ball
（a）Weigh 8 g ferric chloride hexahydrates（FeCl3·6H2O）With 3 g trisodium citrates (Na3Cit·2H2O) it is dissolved in 300 mL
Ethylene glycol obtains orange clear solution；
（b）Toward step（a）15 g sodium acetates are added in obtained solution（NaAc）, continue magnetic agitation to dissolving, acquired solution
It is transferred in reaction kettle, is warming up to 200 DEG C of 12 h of sustained response；
（c）By step（b）Products therefrom is alternately washed each 3 times, after carrying out Magnetic Isolation with magnet with ultra-pure water and absolute ethyl alcohol
Drying obtains Fe3O4Magnetic ball, it is spare；
（Two）Fe3O4The preparation of@PDA core-shell materials
（1）Weigh 0.2 g trishydroxymethylaminomethanes（Tris）It is dissolved in 150 mL secondary waters and is configured to 10 mM buffer solutions, use
Salt acid for adjusting pH is to 8.5；
（2）Weigh 0.35 g steps（One）Fe obtained3O4Magnetic ball ultrasonic disperse is in step（1）In the buffer solution of preparation, after
It is continuous that 0.4 g dopamines are added（DA）, 4 h of mechanical agitation at room temperature；
（3）After the completion of reaction, products therefrom ultra-pure water and absolute ethyl alcohol are alternately washed each 2 times, magnetic point is carried out with magnet
Fe is obtained from rear drying3O4@PDA core-shell materials, it is spare；
（Three）The preparation of core-shell magnetic gamma-cyclodextrin polymer composites
（A）Weigh 2 g gamma-cyclodextrins（γ-CD）, 1 g tetrafluoros terephthalonitrile and 3 g potassium carbonate（K2CO3）It is burnt in two neck round bottoms
In bottle, 60 mL THF/DMF mixed solvents are added（THF:DMF=9:1 v/v）10 min of ultrasonic disperse；0.3 g steps are added
（Two）Fe obtained3O4@PDA core-shell materials continue 10 min of ultrasonic disperse；
（B）By step（A）Gained reactant is heated to 85 DEG C, mechanical agitation and condensing reflux 2 days；
（C）After the completion of reaction, by products therefrom ultra-pure water, THF and dichloromethane（CH2Cl2）Successively supersound washing 15,30,
15 min, room temperature is dried after carrying out Magnetic Isolation with magnet, obtains the core-shell magnetic gamma-cyclodextrin polymer composites
（Fe3O4@PDA@P-CDP）.
Application examples
Adsorbent is extracted using core-shell magnetic gamma-cyclodextrin polymer composites obtained as Magnetic solid phases, in conjunction with liquid phase color
Spectrum-mass spectrometer（HPLC-MS）, it is applied to the extraction of Microcystin in water sample, is as follows：
（i）Core-shell magnetic gamma-cyclodextrin polymer composites are added in the sample containing Microcystin, vortex is passed through
Or shaking mode promotes to adsorb, and with appropriate elution and eluent is collected after Magnetic Isolation, by supernatant and eluent
It is quantified with liquid chromatograph-mass spectrometer；
（ii）Under the chromatography of setting, mass spectrometry method, optimization eluent, adsorbent amount extraction time, elution time, absorption
pH；
（iii）Under conditions of optimal, the investigation of the range of linearity, detection line, sensitivity etc. is carried out to method；
（iiii）Detect the content of Microcystin in actual water sample.
The results are shown in Figure 2, and it is respectively 3 kinds of Microcystin hybrid standard product, warp that Fig. 2 tetra-, which opens chromatogram from top to bottom,
Fe3O4The processed supernatants of@PDA, through Fe3O4The processed supernatants of@PDA@P-CDP, through Fe3O4@PDA@P-CDP are processed
Eluent HPLC chromatogram.It can be seen that through Fe3O4Microcystin is not complete in the processed sample supernatants of@PDA
Full absorption, and through Fe3O4It is then remained substantially without Microcystin in the processed sample supernatants of@PDA@P-CDP, through elution
The Microcystin to get off responds on HPLC close to standard items, therefore, it is considered that synthesized Fe3O4@PDA@P-CDP particles pair
Microcystin has good separation and concentration effect.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification should all belong to the covering scope of the present invention.
Claims (8)
1. a kind of preparation method of core-shell magnetic gamma-cyclodextrin polymer composites, it is characterised in that：Specifically include following step
Suddenly：
（One）Fe3O4The preparation of magnetic ball
（a）It weighs 4-8 g ferric chloride hexahydrates and 2-3 g trisodium citrates is dissolved in 150-300 mL ethylene glycol, obtain orange clear
Clear solution；
（b）Toward step（a）10-15 g sodium acetates are added in obtained solution, continue magnetic agitation to dissolving, acquired solution shifts
To carrying out solvent thermal reaction in reaction kettle；
（c）By step（b）Products therefrom is alternately washed with ultra-pure water and absolute ethyl alcohol, is dried after carrying out Magnetic Isolation with magnet
To Fe3O4Magnetic ball, it is spare；
（Two）Fe3O4The preparation of@PDA core-shell materials
（1）It weighs 0.1-0.2 g trishydroxymethylaminomethanes and is dissolved in 80-150 mL secondary waters and be configured to 10 mM buffer solutions, use
Salt acid for adjusting pH is to 8.5；
（2）Weigh 0.1-0.35 g steps（One）Fe obtained3O4Magnetic ball ultrasonic disperse is in step（1）In the buffer solution of preparation,
0.2-0.4 g dopamines are continuously added, at room temperature mechanical agitation；
（3）After the completion of reaction, products therefrom ultra-pure water and absolute ethyl alcohol are alternately washed, dried after carrying out Magnetic Isolation with magnet
It is dry to obtain Fe3O4@PDA core-shell materials, it is spare；
（Three）The preparation of core-shell magnetic gamma-cyclodextrin polymer composites
（A）1-2 g gamma-cyclodextrins, 0.5-1 g tetrafluoros terephthalonitriles and 2-3 g potassium carbonate are weighed in two neck round-bottom flasks,
50-60 mL THF/DMF mixed solvent ultrasonic disperses are added；0.1-0.3 g steps are added（Two）Fe obtained3O4@PDA nucleocapsids
Material continues ultrasonic disperse；
（B）By step（A）Gained reactant is heated to 85 DEG C, mechanical agitation and condensing reflux 2 days；
（C）After the completion of reaction, by products therefrom ultra-pure water, THF and dichloromethane successively supersound washing, magnetism is carried out with magnet
Room temperature is dried after separation, obtains the core-shell magnetic gamma-cyclodextrin polymer composites.
2. the preparation method of core-shell magnetic gamma-cyclodextrin polymer composites according to claim 1, feature exist
In：In step（One）Fe3O4In the preparation process of magnetic ball, step（b）Described in the technological parameter of solvent thermal reaction be：Reaction
Temperature is 200 DEG C, and the reaction time is 12 h.
3. the preparation method of core-shell magnetic gamma-cyclodextrin polymer composites according to claim 1, feature exist
In：In step（Two）Fe3O4In the preparation process of@PDA core-shell materials, step（2）Described in the mechanical agitation time be 4 h.
4. the preparation method of core-shell magnetic gamma-cyclodextrin polymer composites according to claim 1, feature exist
In：In step（Three）Core-shell magnetic gamma-cyclodextrin polymer composites preparation process in, step（A）Described in THF/
DMF mixed solvents are mixed by solvent THF and DMF, and the volume ratio of wherein THF and DMF are 9:1.
5. the preparation method of core-shell magnetic gamma-cyclodextrin polymer composites according to claim 1, feature exist
In：In step（Three）Core-shell magnetic gamma-cyclodextrin polymer composites preparation process in, step（A）In ultrasound point
It is 10 min to dissipate the time.
6. core-shell magnetic gamma-cyclodextrin polymer composites made from a kind of preparation method as described in claim 1,
It is characterized in that：The composite material is coated layer by layer by poly-dopamine and cyclodextrin；Wherein, cyclodextrin thickness
Degree is 20 nm.
7. core-shell magnetic gamma-cyclodextrin polymer composites answers made from a kind of preparation method as described in claim 1
With, it is characterised in that：The composite material is applied to as Magnetic solid phases extraction adsorbent in conjunction with liquid chromatograph-mass spectrometer
The extraction of Microcystin in water sample.
8. application according to claim 7, it is characterised in that：It is as follows：
（i）Core-shell magnetic gamma-cyclodextrin polymer composites are added in the sample containing Microcystin, vortex is passed through
Or shaking mode promotes to adsorb, and with appropriate elution and eluent is collected after Magnetic Isolation, by supernatant and eluent
It is quantified with liquid chromatograph-mass spectrometer；
（ii）Under the chromatography of setting, mass spectrometry method, optimization eluent, adsorbent amount extraction time, elution time, absorption
pH；
（iii）Under conditions of optimal, the investigation of the range of linearity, detection line, sensitivity etc. is carried out to method；
（iiii）Detect the content of Microcystin in actual water sample.
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Cited By (5)
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| CN110396146A (en) * | 2019-07-11 | 2019-11-01 | 江苏大学 | The preparation method of phenyl boric acid modified magnetic beta cyclo dextrin polymer and its application of Selective Separation shikimic acid |
| CN110433776A (en) * | 2019-07-25 | 2019-11-12 | 湖北大学 | Beta-cyclodextrin functional magnetic carbosphere and preparation method |
| CN113058571A (en) * | 2021-03-23 | 2021-07-02 | 南昌大学 | Preparation method of bifunctional polymer adsorbent and application of bifunctional polymer adsorbent in gold recovery |
| CN113144219A (en) * | 2021-04-26 | 2021-07-23 | 燕山大学 | Sulfydryl modified beta-cyclodextrin-polydopamine nanosphere and preparation method and application thereof, drug loading system and preparation method thereof |
| CN114772944A (en) * | 2022-04-22 | 2022-07-22 | 福州大学 | Solvent-resistant adhesion-adjustable photoresponse surface and preparation method thereof |
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| CN110396146A (en) * | 2019-07-11 | 2019-11-01 | 江苏大学 | The preparation method of phenyl boric acid modified magnetic beta cyclo dextrin polymer and its application of Selective Separation shikimic acid |
| CN110396146B (en) * | 2019-07-11 | 2021-05-25 | 江苏大学 | Preparation method of phenylboronic acid modified magnetic beta-cyclodextrin polymer and application of phenylboronic acid modified magnetic beta-cyclodextrin polymer in selective separation of shikimic acid |
| CN110433776A (en) * | 2019-07-25 | 2019-11-12 | 湖北大学 | Beta-cyclodextrin functional magnetic carbosphere and preparation method |
| CN113058571A (en) * | 2021-03-23 | 2021-07-02 | 南昌大学 | Preparation method of bifunctional polymer adsorbent and application of bifunctional polymer adsorbent in gold recovery |
| CN113144219A (en) * | 2021-04-26 | 2021-07-23 | 燕山大学 | Sulfydryl modified beta-cyclodextrin-polydopamine nanosphere and preparation method and application thereof, drug loading system and preparation method thereof |
| CN114772944A (en) * | 2022-04-22 | 2022-07-22 | 福州大学 | Solvent-resistant adhesion-adjustable photoresponse surface and preparation method thereof |
| CN114772944B (en) * | 2022-04-22 | 2023-06-23 | 福州大学 | Solvent-resistant adhesion-adjustable photoresponsive surface and preparation method thereof |
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Application publication date: 20180828 |