CN102489269B - Preparation method of glibenclamide magnetic nano silica gel surface polyamide-amide dendritic molecular imprinting polymer - Google Patents

Preparation method of glibenclamide magnetic nano silica gel surface polyamide-amide dendritic molecular imprinting polymer Download PDF

Info

Publication number
CN102489269B
CN102489269B CN 201110426440 CN201110426440A CN102489269B CN 102489269 B CN102489269 B CN 102489269B CN 201110426440 CN201110426440 CN 201110426440 CN 201110426440 A CN201110426440 A CN 201110426440A CN 102489269 B CN102489269 B CN 102489269B
Authority
CN
China
Prior art keywords
glibenclamide
silica gel
nano silica
magnetic nano
polyamide
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
Application number
CN 201110426440
Other languages
Chinese (zh)
Other versions
CN102489269A (en
Inventor
周学敏
王若禹
王舒
文婷婷
汪洋
薛诚
洪俊丽
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nanjing University
Nanjing Medical University
Original Assignee
Nanjing Medical University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nanjing Medical University filed Critical Nanjing Medical University
Priority to CN 201110426440 priority Critical patent/CN102489269B/en
Publication of CN102489269A publication Critical patent/CN102489269A/en
Application granted granted Critical
Publication of CN102489269B publication Critical patent/CN102489269B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Abstract

The invention discloses a preparation method of a glibenclamide magnetic nano silica gel surface polyamide-amide (PAMAM) dendritical molecular imprinting polymer, which comprises the following steps of: (1) dendritically and functionally grafting Fe3O4@SiO2; (2) placing a template molecule, a functional monomer and the functionally grafted Fe3O4@SiO2 in a porogenic agent for prepolymerization, adding a cross-linking agent and an initiating agent, and polymerizing the materials under the reflux of nitrogen; and (3) eluting the polymer to remove a template molecule using a methanol hydrochloric acid solution. The glibenclamide magnetic nano silica gel surface polyamide-amide dendritical molecular imprinting polymer prepared in the invention has specific recognition capability on glibenclamide and drugs with similar structure thereof. The glibenclamide magnetic nano silica gel surface polyamide-amide dendritical molecular imprinting polymer is used together with chromatography and can be used for the fast separation, enrichment and measurement of glibenclamide illegally added into health foods and drugs.

Description

The preparation method of glibenclamide magnetic Nano silica gel surface polyamide-amide dendrimer imprinted polymer
Technical field
The invention belongs to new material technology field, be specifically related to the preparation method of glibenclamide magnetic Nano silica gel surface polyamide-amide dendrimer imprinted polymer.
Background technology
Current food and drug safety has become global focal issue.Especially in health food and Chinese medicine preparation, add the illegal activities that chemicals increases its effect, cause that because it has more disguise, duplicity and harmfulness the whole society greatly pays close attention to, add glibenclamide, Glimepiride and Glipizide etc. as regulating in blood sugar class health food and the Chinese medicine preparation.
Diabetes are one of incidence of disease disease with high in the world at present.The hypoglycemic medicine that is used for the treatment of diabetes on the market is more, glibenclamide (Glibenclamide wherein, claim glibenclamide again) be second generation sulfonylureas OHA, its curative effect characteristics are blood sugar reducing function appearance effect in strong, oral back 30 minutes, continue about 16-24 hour.But the patient is overdose under unwitting situation, can occur a series of as serious adverse reactions such as hepatic disorder, decrease of platelet, hypoglycemic reactions, even threat to life.In recent years, some lawless persons are ordered about by interests, add chemical medicine compositions such as glibenclamide without authorization in Chinese patent drug, cause the illusion of quick acting.Present various novel detection analytical instrument, the chromatography of gases and the liquid chromatogram that particularly have mass detector all are being greatly improved aspect applicability and the sensitivity.But because forbidden drug content is low in health products or the Chinese patent drug, and complex matrices composition (especially compound Chinese herbal medicinal ingredients) phase mutual interference, exist sample preparation methods and pre-treatment process numerous and diverse more, lack problems such as selective.Therefore, be necessary to set up a kind of quick, sensitive, accurate, reliable analytical method.
Molecularly imprinted polymer (Molecular Imprinted Polymers, MIPs) to " identification " effect of " memory " effect of template molecule space structure and action site, a kind of target molecule or one group of analogue molecule in can high selectivity separation and concentration complex system.In environment, food, agricultural chemicals and Pharmaceutical Analysis, more application is arranged.But, along with going deep into of molecular imprinting research, when MIPs shows originality, also present the new problem that needs solution in various analytical technologies.Absorption, elution requirement selection and flow velocity control etc. as the molecular imprinting SPE are comparatively loaded down with trivial details.Given this we have introduced magnetic separation technique, magnetic separation technique is the magnetic characteristics of utilizing magnetic Nano material, by the finishing to nano particle, the surface ligand of magnetic nano-particle is realized separating fast the target target with interaction between the acceptor, it is a kind of new separation technology based on solid phase carrier, can save numerous and diverse operations such as centrifugal, filtration, make the separation of solid-liquid phase very simple fast, this all brings very big facility for the preparation of nanometer marking material and application.
Along with deepening continuously of nano-material surface MIPs research, this deep-seated problem of marking efficient of MIPs nuclear shell represents gradually, and the research of nano-material surface functional graft is its key link, enjoys attention, but does not see breakthrough.Dendritic (dendrimers) is a class novel high polymer nano material, and its potential using value has caused scientist's extensive concern.Dendritic macromole is the research focus of field of polymer technology always, its compound with regular structure, symmetry, zero defect, spherical in shape, its molecular volume, functional group kind and number are all accurately controlled, distribution has monodispersity, and have particular structure characteristics such as topology structure, make it demonstrate wide potential application foreground in various fields such as membrane material, nano composite material, biological medicine carrier, catalyst.Wherein polyamide-amide (PAMAM) is one of maximum dendritic macromole of research at present, contain a large amount of amino functional groups (uncle's ammonia on the dendritic surface of PAMAM, uncle's ammonia, acyl ammonia etc.), and the number of these functional groups increases along with minute subalgebra increases with geometric progression, and internal layer has a large amount of cavitys, and the synthetic mass efficient site that provides of molecularly imprinted polymer is provided, therefore, molecular imprinting and PAMAM dendritic macromole is combined into the research hot issue.
Molecule at glibenclamide, crossing research by surface molecular imprinted technology, magnetic separation technique and PAMAM dendritic macromole, prepare glibenclamide is had high sensitivity, high selectivity magnetic Nano silica gel surface dendrimer imprinted polymer, significant to the violated interpolation monitoring of glibenclamide and analogue thereof.
Summary of the invention
The objective of the invention is to overcome the preparation method that above-mentioned weak point provides a kind of glibenclamide magnetic Nano silica gel surface polyamide-amide dendrimer imprinted polymer.
The objective of the invention is to realize in the following manner:
A kind of glibenclamide magnetic Nano silica gel surface polyamide-amide dendrimer imprinted polymer preparation method is characterized in that this method may further comprise the steps:
A) .Fe 3O 4@SiO 2Functional graft: with Fe 3O 4@SiO 2Nanoparticle is scattered in the toluene, add silane coupler, add hot reflux 12~48h under the condition of nitrogen gas, after Magnetic Isolation, washing, under the nitrogen protection, be solvent with methyl alcohol, intersect heating reflux reaction with methyl acrylate and ethylenediamine, respectively with methyl acrylate and reacting ethylenediamine 1~3 time, each reaction 24~36h obtains magnetic Nano silica gel surface polyamide-amide dendrimer;
B). template molecule glibenclamide and magnetic Nano silica gel surface polyamide-amide dendrimer are placed pre-polymerization 0.5~2h under the pore-foaming agent room temperature, add trifluoromethyl acrylate (TFMAA) room temperature pre-polymerization 0.5~2h again, add crosslinking agent and initator at last, under the nitrogen protection, successively at 50 ℃ of following polymerization 6~24h, 60 ℃ of following polymerization 12~36h, 85 ℃ of following polymerization 6~36h;
C). resulting polymers is with 1~4mol L -1Hydrochloric acid methanol mixed solution (preferred 2mol L -1The hydrochloric acid methanol mixed solution) wash-out template molecule, drying obtain glibenclamide magnetic Nano silica gel surface polyamide-amide dendrimer imprinted polymer.
The concentration of commercially available hydrochloric acid is generally 12mol/L, namely prepares every liter of 1~4mol/L hydrochloric acid methanol mixed solution and need use hydrochloric acid 0.0833~0.3333 (L), adds methyl alcohol 0.6667~0.9167 (L) and gets final product.
Described Fe 3O 4@SiO 2The ratio of nanoparticle and silane coupler is 1: 0.08~0.16 (g/mol), and silane coupler is the gamma-aminopropyl-triethoxy-silane of volume ratio 1: 1~3 and the mixture of gamma-methyl allyl acyloxypropyl trimethoxysilane.The mol ratio of methyl acrylate and ethylenediamine is 1: 1, and the mol ratio of methyl acrylate and silane coupler is 1~7: 1~2.Described adding silane coupler, the heating reflux temperature is 40~80 ℃ under the condition of nitrogen gas.
Described crosslinking agent is ethylene glycol dimethacrylate (EGDMA); Initator is azodiisobutyronitrile; Pore-foaming agent is toluene or methyl alcohol.Described template molecule glibenclamide is 2.5~10mmol L in the concentration of pore-foaming agent -1Template molecule glibenclamide, trifluoromethyl acrylate, crosslinking agent three's mol ratio is 1: 1~12: 2~48, and the mole of initator is 10%~20% of template molecule glibenclamide mole.The usage ratio of glibenclamide and magnetic Nano silica gel surface polyamide-amide dendrimer is 0.1~0.5/25~55 (mmol/mg), preferred 0.26/40 (mmol/mg).
Fe of the present invention 3O 4@SiO 2Preparation can carry out according to following steps: with sol-gel process at Fe 3O 4Nanoparticle surface parcel SiO 2Adopt alcohol reagent as dispersant, under the ammonia-catalyzed effect, the hydrolysis esters of silicon acis produces condensation reaction, at Fe 3O 4The nanoparticle surface forms silica top layer structure, and ultra-pure water washing and purifying obtain Fe 3O 4@SiO 2Composite nano-granule.Described alcohol reagent is preferably isopropyl alcohol; Esters of silicon acis is ethyl orthosilicate (TEOS).
The present invention is with Fe 3O 4@SiO 2Nanoparticle is scattered in the toluene, adds an amount of silane coupler and carries out functional graft, makes it contain the amino and two keys of required active group, intersects heating reflux reaction with methyl acrylate and ethylenediamine again.The 2nd time during with methyl acrylate and ethylenediamine heating reflux reaction, the consumption of methyl acrylate and ethylenediamine is two times of the 1st secondary response, the 3rd time during with methyl acrylate and ethylenediamine heating reflux reaction, the consumption of methyl acrylate and ethylenediamine is two times of the 2nd secondary response, obtains being rich in amino magnetic Nano silica gel surface polyamide-amide dendrimer.
Beneficial effect of the present invention compared with the prior art:
1. the present invention is with Fe 3O 4As the nano material core, the preparation of MIPs and application are become more economically, convenient and environmental protection, the layer of silica gel of magnetic nano particle surface parcel is not only Fe 3O 4The modifier of nanoparticle and stabilizing agent, and by the orientation effect that plays surface grafting the MIPs recognition site is evenly distributed, simultaneously make the MIPs nanostructured have high degree of rigidity and stability as carrier, magnetic separation technique also provides new thinking for the development of dendritic macromole and molecular imprinting.
2. the dendritic polyamide-amide of the present invention preparation, raw material sources are extensive, low price, simple synthetic method, preparation cost is cheap, and gained is organic-and the polymer composite outer end contains a large amount of amino, the synthetic mass efficient group that provides of molecularly imprinted polymer is provided, organically combine with Magnetic Isolation, can effectively solve problems such as the organic synthesis separating step is loaded down with trivial details.
3. the magnetic Nano silica gel surface glibenclamide polyamide-amide dendrimer imprinted polymer of the present invention's preparation has higher magnetic (Fe 3O 4, Fe 3O 4@SiO 2And MIPs magnetic is respectively 80.23,30.65,13.23emu g -1), effective rate of utilization is higher, characteristics such as adsorbance height.
4. the molecularly imprinted polymer of the present invention preparation and chromatograph joint used can be used for quick separation and the enrichment of glibenclamide and analogue in the complex matrices, and the high selectivity, the high sensitivity that finally reach sample are accurately measured.
Description of drawings
Fig. 1: the static adsorption curve of glibenclamide magnetic Nano silica gel surface polyamide-amide dendrimer imprinted polymer.
Fig. 2: glibenclamide magnetic Nano silica gel surface polyamide-amide dendrimer imprinted polymer curve of adsorption kinetics.
Fig. 3: glibenclamide magnetic Nano silica gel surface polyamide-amide dendrimer imprinted polymer desorption kinetic curve.
Fig. 4: the synthetic schematic diagram of glibenclamide magnetic Nano silica gel surface polyamide-amide dendrimer imprinted polymer.
The specific embodiment
Below by specific embodiment the present invention is further elaborated, should not be construed as limited overall technical solution.
Embodiment 1
Preparation Fe 3O 4@SiO 2Nanoparticle
In the 250mL three-necked bottle, add 80mL deoxygenation deionized water, add FeCl under the nitrogen protection 36H 2O (4.72g) and FeCl 24H 2O (1.98g), 800rmp/min stirs, and 85 ℃ dropwise add concentrated ammonia liquor 15mL, oleic acid 1mL, reaction 1h, Magnetic Isolation gets the Fe of black 3O 4Nanoparticle, deionized water are washed till neutral standby;
Get 0.3g Fe 3O 4Nanoparticle is dispersed in 30mL isopropyl alcohol and the 2mL deionized water, keeps the 200rmp/min mixing speed, adds 2mL concentrated ammonia liquor and the positive tetraethyl orthosilicate of 5mL (TEOS), room temperature reaction 12h, and Magnetic Isolation gets Fe 3O 4@SiO 2Nanoparticle, deionized water is washed till neutrality, dry for standby;
Embodiment 2
1, Fe 3O 4@SiO 2The nanoparticle functional graft:
Get the Fe that 0.1g prepares according to embodiment 1 method 3O 4@SiO 2Nanoparticle is scattered in the 50mL toluene, adds 1mL gamma-aminopropyl-triethoxy-silane and 1mL gamma-methyl allyl acyloxypropyl trimethoxysilane, nitrogen adds hot reflux 24~36h for following 60 ℃, through Magnetic Isolation, uses toluene, methanol wash successively, vacuum drying obtains the Fe of functional modification 3O 4@SiO 2Nanoparticle;
2, the preparation of magnetic Nano silica gel surface polyamide-amide dendrimer:
Get the Fe of functional modification 3O 4@SiO 2Nanoparticle adds 50mL methyl alcohol and 0.75mL methyl acrylate (MA), under nitrogen protection, adds hot reflux 24~36h, through Magnetic Isolation, uses methanol wash, vacuum drying; Subsequently, add 50mL methyl alcohol and 0.60mL ethylenediamine (EDA), under nitrogen protection, add hot reflux 24~36h, through Magnetic Isolation, use methanol wash, vacuum drying, repeat above-mentioned respectively with the step of methyl acrylate and reacting ethylenediamine once, the consumption of the 2nd secondary response methyl acrylate and ethylenediamine is 2 times of the 1st secondary response, namely gets magnetic Nano silica gel surface polyamide-amide dendritic macromole;
3, the preparation of glibenclamide magnetic Nano silica gel surface polyamide-amide dendritic macromole imprinted polymer:
0.26mmol glibenclamide and 40mg magnetic polyamide-amide dendritic macromole pre-polymerization 1h under the room temperature in 50mL methyl alcohol; add the 36.5mg trifluoromethyl acrylate subsequently; pre-polymerization 1h under the room temperature; add 392 μ L ethylene glycol dimethacrylates and 30mg azodiisobutyronitrile (mol ratio that makes template molecule, function monomer, crosslinking agent three is 1: 1: 8) then; under nitrogen protection; react 6h successively under 50 ℃, 60 ℃ are reacted 24h down, and 85 ℃ are reacted 8h down.After reaction finishes, polymer 2mol L -1Hydrochloric acid methanol mixed solution wash-out template molecule, vacuum drying obtain glibenclamide magnetic Nano silica gel surface polyamide-amide dendritic macromole imprinted polymer.
Take by weighing 20~50mg glibenclamide magnetic Nano silica gel surface polyamide-amide dendrimer imprinted polymer (MIPs) and blank glibenclamide magnetic Nano silica gel surface polyamide-amide dendrimer imprinted polymer (NIPs, for except not adding the template molecule, its preparation process is consistent with MIPs) place conical flask, add 5~10mL, 0.06~8mmol L respectively -1Glibenclamide solution, sealing is vibrated under the room temperature, reach adsorption equilibrium after, Magnetic Isolation supernatant, supernatant utilize HPLC-UV to measure concentration, calculate MIPs and the NIPs adsorption capacity Q under variable concentrations respectively, the results are shown in Figure 1.As seen from Figure 1, MIPs maximal absorptive capacity Q is 167.62 μ mol g -1, NIPs maximal absorptive capacity Q is 57.49 μ mol g -1, MIPs is about 3 times of NIPs adsorbance.
Take by weighing the some parts of 20~50mg MIPs in conical flask, add 5~10mL 8mmol L respectively -1Glibenclamide solution and vibrates under the room temperature, separation of supernatant under 5~60min outside magnetic field, and supernatant is measured concentration by HPLC-UV, calculates MIPs respectively at the adsorbance Q of different time to glibenclamide, the results are shown in Figure 2.As seen from Figure 2, MIPs namely reaches adsorption equilibrium at 40min.
Take by weighing the some parts of 20~50mg MIPs in conical flask, add 5~10mL 8mmol L respectively -1Vibrate to adsorption equilibrium under the glibenclamide solution, room temperature, isolated for disposal supernatant under the external magnetic field, drying adds 2mol L -1The time that the ultrasonic desorb of methanol hydrochloride solution is different, stripping liquid utilizes HPLC-UV to measure concentration, draws to reach the required time of balance, the results are shown in Figure 3.As seen from Figure 3, the MIPs desorb of having adsorbed glibenclamide only needs 25min.
Embodiment 3
1, Fe 3O 4@SiO 2The nanoparticle functional graft:
Get the Fe that 0.1g prepares according to embodiment 1 method 3O 4@SiO 2Nanoparticle is scattered in the 50mL toluene, adds 1mL gamma-aminopropyl-triethoxy-silane and 3mL gamma-methyl allyl acyloxypropyl trimethoxysilane, nitrogen adds hot reflux 24~36h for following 50 ℃, through Magnetic Isolation, uses toluene, methanol wash successively, vacuum drying obtains the Fe of functional modification 3O 4@SiO 2Nanoparticle;
2, the preparation of magnetic Nano silica gel surface polyamide-amide dendrimer:
Get the Fe of functional modification 3O 4@SiO 2Nanoparticle adds 50mL methyl alcohol and 0.75mL methyl acrylate (MA), under nitrogen protection, adds hot reflux 24~36h, through Magnetic Isolation, uses methanol wash, vacuum drying; Subsequently, add 50mL methyl alcohol and 0.60mL ethylenediamine (EDA), under nitrogen protection, add hot reflux 24~36h, through Magnetic Isolation, use methanol wash, vacuum drying namely gets magnetic Nano silica gel surface polyamide-amide dendritic macromole;
3, the preparation of glibenclamide magnetic Nano silica gel surface polyamide-amide dendritic macromole imprinted polymer:
0.26mmol glibenclamide and 55mg magnetic polyamide-amide dendritic macromole pre-polymerization 2h under the room temperature in 50mL methyl alcohol; add trifluoromethyl acrylate subsequently; pre-polymerization 2h under the room temperature; add ethylene glycol dimethacrylate and 30mg azodiisobutyronitrile (mol ratio that makes template molecule, function monomer, crosslinking agent three is 1: 5: 16) then; under nitrogen protection; react 24h successively under 50 ℃, 60 ℃ are reacted 12h down, and 85 ℃ are reacted 16h down.After reaction finishes, polymer 1molL -1Hydrochloric acid methanol mixed solution wash-out template molecule, vacuum drying obtain glibenclamide magnetic Nano silica gel surface polyamide-amide dendrimer imprinted polymer.
Embodiment 4
1, Fe 3O 4@SiO 2The nanoparticle functional graft:
Get the Fe that 0.1g prepares according to embodiment 1 method 3O 4@SiO 2Nanoparticle is scattered in the 50mL toluene, adds 1mL gamma-aminopropyl-triethoxy-silane and 2mL gamma-methyl allyl acyloxypropyl trimethoxysilane, nitrogen adds hot reflux 24~36h for following 80 ℃, through Magnetic Isolation, uses toluene, methanol wash successively, vacuum drying obtains the Fe of functional modification 3O 4@SiO 2Nanoparticle;
2, the preparation of magnetic Nano silica gel surface polyamide-amide dendrimer:
Get the Fe of functional modification 3O 4@SiO 2Nanoparticle adds 50mL methyl alcohol and 0.75mL methyl acrylate (MA), under nitrogen protection, adds hot reflux 24~36h, through Magnetic Isolation, uses methanol wash, vacuum drying; Subsequently, add 50mL methyl alcohol and 0.60mL ethylenediamine (EDA), under nitrogen protection, add hot reflux 24~36h, through Magnetic Isolation, use methanol wash, vacuum drying, repeat above-mentioned respectively with the step 2 of methyl acrylate and reacting ethylenediamine time, the 2nd time the consumption of methyl acrylate and ethylenediamine is 2 times of the 1st secondary response during with methyl acrylate and ethylenediamine heating reflux reaction, and the 3rd time during with methyl acrylate and ethylenediamine heating reflux reaction, the consumption of methyl acrylate and ethylenediamine is 2 times of the 2nd secondary response, namely gets magnetic Nano silica gel surface polyamide-amide dendritic macromole;
3, the preparation of glibenclamide magnetic Nano silica gel surface polyamide-amide dendritic macromole imprinted polymer:
0.26mmol glibenclamide and 55mg magnetic polyamide-amide dendritic macromole pre-polymerization 1.5h under the room temperature in 50mL methyl alcohol; add trifluoromethyl acrylate subsequently; pre-polymerization 1.5h under the room temperature; add ethylene glycol dimethacrylate and 30mg azodiisobutyronitrile (mol ratio that makes template molecule, function monomer, crosslinking agent three is 1: 10: 24) then; under nitrogen protection; react 16h successively under 50 ℃, 60 ℃ are reacted 16h down, and 85 ℃ are reacted 10h down.After reaction finishes, polymer 4mol L -1Hydrochloric acid methanol mixed solution wash-out template molecule, vacuum drying obtain glibenclamide magnetic Nano silica gel surface polyamide-amide dendrimer imprinted polymer.

Claims (8)

1. glibenclamide magnetic Nano silica gel surface polyamide-amide dendrimer imprinted polymer preparation method is characterized in that this method may further comprise the steps:
With Fe 3O 4@SiO 2Nanoparticle is scattered in the toluene, adds silane coupler, adds hot reflux 12~48h under the condition of nitrogen gas, after Magnetic Isolation, and washing, vacuum drying; Under the nitrogen protection, be solvent with methyl alcohol, intersect heating reflux reaction with methyl acrylate and ethylenediamine, with methyl acrylate and reacting ethylenediamine 1~3 time, react 24~36h respectively at every turn, obtain magnetic Nano silica gel surface polyamide-amide dendrimer;
Template molecule glibenclamide and magnetic Nano silica gel surface polyamide-amide dendrimer are placed pre-polymerization 0.5~2h under the pore-foaming agent room temperature, add trifluoromethyl acrylate room temperature pre-polymerization 0.5~2h again, add crosslinking agent and initator at last, under the nitrogen protection, successively at 50 ℃ of following polymerization 6~24 h, 60 ℃ of following polymerization 12~36h, 85 ℃ of following polymerization 6~36h;
Resulting polymers is with 1~4mol L -1Hydrochloric acid methanol mixed solution wash-out template molecule, drying obtains glibenclamide magnetic Nano silica gel surface polyamide-amide dendrimer imprinted polymer.
2. according to the surface of the glibenclamide magnetic Nano silica gel described in the claim 1 polyamide-amide dendrimer imprinted polymer preparation method, it is characterized in that: described Fe 3O 4@SiO 2The ratio of nanoparticle and silane coupler is 1:0.08~0.16g/mol, and silane coupler is the gamma-aminopropyl-triethoxy-silane of volume ratio 1:1~3 and the mixture of gamma-methyl allyl acyloxypropyl trimethoxysilane.
3. according to the surface of the glibenclamide magnetic Nano silica gel described in the claim 1 polyamide-amide dendrimer imprinted polymer preparation method, it is characterized in that: the mol ratio of described methyl acrylate and ethylenediamine is 1:1, and the mol ratio of methyl acrylate and silane coupler is 1~7:1~2.
4. according to the surface of the glibenclamide magnetic Nano silica gel described in the claim 1 polyamide-amide dendrimer imprinted polymer preparation method, it is characterized in that: described adding silane coupler, the heating reflux temperature is 40~80 ℃ under the condition of nitrogen gas.
5. according to the surface of the glibenclamide magnetic Nano silica gel described in the claim 1 polyamide-amide dendrimer imprinted polymer preparation method, it is characterized in that: described crosslinking agent is ethylene glycol dimethacrylate; Initator is azodiisobutyronitrile; Pore-foaming agent is toluene or methyl alcohol.
6. according to the surface of the glibenclamide magnetic Nano silica gel described in the claim 1 polyamide-amide dendrimer imprinted polymer preparation method, it is characterized in that: described template molecule glibenclamide is 2.5~10 mmol L in the concentration of pore-foaming agent -1
7. according to the surface of the glibenclamide magnetic Nano silica gel described in the claim 1 polyamide-amide dendrimer imprinted polymer preparation method, it is characterized in that: template molecule glibenclamide, trifluoromethyl acrylate, crosslinking agent three's mol ratio is 1:1~12:2~48, and the mole of initator is 10%~20% of template molecule glibenclamide mole.
8. according to the surface of the glibenclamide magnetic Nano silica gel described in the claim 1 polyamide-amide dendrimer imprinted polymer preparation method, it is characterized in that: the usage ratio of glibenclamide and magnetic Nano silica gel surface polyamide-amide dendrimer is 0.1~0.5/25~55mmol/mg.
CN 201110426440 2011-12-19 2011-12-19 Preparation method of glibenclamide magnetic nano silica gel surface polyamide-amide dendritic molecular imprinting polymer Expired - Fee Related CN102489269B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 201110426440 CN102489269B (en) 2011-12-19 2011-12-19 Preparation method of glibenclamide magnetic nano silica gel surface polyamide-amide dendritic molecular imprinting polymer

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 201110426440 CN102489269B (en) 2011-12-19 2011-12-19 Preparation method of glibenclamide magnetic nano silica gel surface polyamide-amide dendritic molecular imprinting polymer

Publications (2)

Publication Number Publication Date
CN102489269A CN102489269A (en) 2012-06-13
CN102489269B true CN102489269B (en) 2013-08-28

Family

ID=46181153

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 201110426440 Expired - Fee Related CN102489269B (en) 2011-12-19 2011-12-19 Preparation method of glibenclamide magnetic nano silica gel surface polyamide-amide dendritic molecular imprinting polymer

Country Status (1)

Country Link
CN (1) CN102489269B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104558628B (en) * 2013-10-17 2017-08-11 中国石油化工股份有限公司 A kind of magnetic Nano grade resins compound and preparation method and application
CN105565329B (en) * 2016-03-17 2017-09-12 杨丽 A kind of preparation method of the powered beer silica gel particle of macropore
CN106975516B (en) * 2017-03-24 2019-06-04 西北工业大学 The preparation method of magnetic rodlike high temperature resistant phase transfer catalyst
CN108753761A (en) * 2018-05-30 2018-11-06 北京理工大学珠海学院 A kind of preparation method of amination modified composite magnetic nano-carrier for lipase immobilization
CN115505163B (en) * 2022-10-17 2024-01-26 云南中烟工业有限责任公司 Surface dendritic magnetic molecularly imprinted material, preparation method and application thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101811033B (en) * 2009-11-13 2012-07-25 南京医科大学 Method for preparing organophosphorus insecticide nano silica gel surface molecular imprinted polymer

Also Published As

Publication number Publication date
CN102489269A (en) 2012-06-13

Similar Documents

Publication Publication Date Title
Zhou et al. Recent advances and trends of molecularly imprinted polymers for specific recognition in aqueous matrix: Preparation and application in sample pretreatment
CN102489269B (en) Preparation method of glibenclamide magnetic nano silica gel surface polyamide-amide dendritic molecular imprinting polymer
Liu et al. A novel smart microsphere with magnetic core and ion-recognizable shell for Pb2+ adsorption and separation
CN104479072B (en) A kind of method preparing magnetic molecularly imprinted adsorbent
Cheong et al. Molecular imprinted polymers for separation science: A review of reviews
Yan et al. Characteristic and synthetic approach of molecularly imprinted polymer
Li et al. Core–shell metal–organic frameworks as the mixed-mode stationary phase for hydrophilic interaction/reversed-phase chromatography
Kempe et al. Development and evaluation of spherical molecularly imprinted polymer beads
Mafu et al. Ion-imprinted polymers for environmental monitoring of inorganic pollutants: synthesis, characterization, and applications
CN103965419B (en) A kind of separation, the magnetic blotting method for producing polymer of purification Ractopamine
CN104028007B (en) A kind of imidazole ion liquid capillary monolithic column and preparation thereof and application
CN102702429A (en) Method for preparing bisphenol A molecularly imprinted polymer
CN102127182B (en) Method for preparing magnetic molecule mark polymer for detecting PDE-5 inhibitor
CN104014320A (en) Aqueous phase metal organic framework molecular imprinting material of enriched trace meta-tolyl-N-methylcarbamate (MTMC)
CN102489273B (en) Preparation method of magnetic beads of dendritic molecular imprinting polymer on surface of estrogenic nano silica gel
CN101845127B (en) Method for preparing core-shell structured composite nano surface molecular imprinting polymer of tanshinone compound
CN106731005B (en) A kind of organic polymer integral post of specific recognition ochratoxin and preparation method thereof
Li et al. Recent development and application of solid phase extraction materials
Chen et al. Synthesis and characterization of photo‐responsive magnetic molecularly imprinted microspheres for the detection of sulfonamides in aqueous solution
CN106040204A (en) Magnetic microporous organic nanotube hybrid material and preparation and application thereof
Zhu et al. Preparation of surface-imprinted polymer magnetic nanoparticles with miniemulsion polymerization for recognition of salicylic acid
CN104910339A (en) Magnetic molecular imprinting polyion liquid for detecting ractopamine as well as preparation method and application of magnetic molecular imprinting polyion liquid
Zhou et al. Preparation, characterization, and Ce (III) adsorption performance of poly (allylamine)/silica composite
CN105044254B (en) The preparation method and application of itrofurans molecular blotting polymer microsphere
CN104140501B (en) A kind of temperature sensitive bisphenol-A imprinted polymer microsphere and application thereof

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
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20130828

Termination date: 20141219

EXPY Termination of patent right or utility model