CN107353372A - A kind of preparation method of the uncoupler imprint surface polymer of nNOS PSD 95 based on magnetic mesoporous molecular sieve - Google Patents
A kind of preparation method of the uncoupler imprint surface polymer of nNOS PSD 95 based on magnetic mesoporous molecular sieve Download PDFInfo
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Abstract
A kind of preparation method of the uncoupler imprint surface polymer of nNOS PSD 95 based on magnetic mesoporous molecular sieve, belongs to molecularly imprinted polymer technical field, specific steps are divided into：Prepare the magnetic mesoporous molecular sieve of core shell structure；Surface graft modification is carried out to obtained magnetic mesoporous silicon dioxide microsphere；Prepare the uncoupler imprint surface polymer of nNOS PSD 95 based on magnetic mesoporous molecular sieve.The uncoupler imprint surface polymer monodispersities of nNOS PSD 95 based on magnetic mesoporous molecular sieve prepared by the present invention are good, specific surface area is big, it is mesoporous regular, with excellent adsorption and desorption dynamics, and polymer stabilisation, favorable reproducibility, to realize that the capture of the selectivity of the uncouplers of nNOS PSD 95 in Chinese medicine and high frequency zone provide possibility.
Description
Technical field
The invention belongs to molecularly imprinted polymer technical field, more particularly to there is the magnetic of specific recognition to ZL006
The preparation method of mesopore molecular sieve imprint surface polymer.
Background technology
Cerebral infarction (cerebral arterial thrombosis) has the characteristics that high mortality, high disability rate, high relapse rate, seriously endangers the mankind
Health.Under the conditions of cerebral ischemia, excitatory amino acid (such as glutamic acid) excessively discharges, and causes NMDA acceptor
(NMDAR) excessive activation, nitric oxide (NO) is discharged by NMDAR-PSD-95-nNOS approach pathologic, so as to cell
Cause major injury.Research finds, nNOS-PSD-95 uncouplers 4- (2- hydroxyl -3,5- benzyl dichlorides amido) -2- hydroxy benzenes first
Sour (ZL006) has clear and definite Cerebral ischemia protection effect (Nature Medicine 2010,16,12：1439-U123), target spot
Clearly, Small side effects, but because its hydrophily is larger, brain tissue distribution is undesirable, to develop into clinical treatment cerebral infarction medicine, also
Require further study and improve.Chinese medicine is the crystallization of thousands of years clinical application experiences of the people, and nNOS- is screened from Chinese medicine
PSD-95 uncouplers, there is the advantages that curative for effect, toxic side effect is small, and druggability is strong.And to block nNOS's and PSD-95
It is coupled as target spot, the research of nNOS-PSD-95 uncouplers is developed from Chinese medicine, there is not been reported.Due to traditional Chinese medicine ingredients are complicated,
Various structures, interfering component are more, so the high frequency zone of its active component is there is an urgent need to a kind of high selectivity, it is specific single-minded
Modern method for separating and detecting.
Recently, will most have can for the development of molecularly imprinted polymer (molecular imprinted polymers, MIPs)
Powerful override and efficient selection can be provided for our screening active ingredients work, MIPs is target molecule " degree body system
Make ", there is specific recognition to template molecule, make the corresponding molecular imprinting of templated synthesis with the bioactive molecule with target drug effect
Polymer, the research of Chinese medical extract is used it for, directly can be screened from the various component storehouse of configuration and template molecule
Composition with identical physiologically active, so as to avoid the non-specificity of traditional separation and Extraction and inefficiencies, substantially increase medicine
The efficiency of thing screening.Although the preparation method of nNOS-PSD-95 uncoupler molecularly imprinted polymers has been reported (Chinese patent
CN201019026093.4), but it belongs to polymerisation in bulk, the MIPs of synthesis exist low " marking " capacity, site " embedding " and
Complicated process steps etc. are short of, and mesopore molecular sieve imprint surface polymer has unique advantage by comparison：(1) heat endurance
And good hydrothermal stability；(2) specific surface area is larger so that Silica Surface forms the more MIPs marking " hole ", prepares
Template molecule residual greatly reduces during MIPs, adds effective " marking " capacity and reduces resistance to mass tranfer, has good suction
Echo analytical dynamics characteristic；(3) regular vertical channel structure is more beneficial for the absorption and release of molecule；(4) aperture
It is adjustable to be distributed homogeneous and size；(5) surface is easy to grafting, chemical modification and functionalized design；(6) preparation is convenient, granularity is controllable；
(7) cheap and environmental protection.
In addition, present invention further introduces Magnetic Isolation (magnetic separation, MS) technology, by magnetic, mesoporous
The combination of molecular sieve and surface molecular imprinted technology, it can be realized under external magnetic field and the quick of target substance is directly divided
From eliminating numerous and diverse operation such as centrifugation, filtering, accelerate separating rate, the time of screening compound is effectively shortened, in being
The selective fast separating concentration of pharmaceutically active substance provides a kind of new strong means with detection.
The content of the invention
The technical problem of solution：For the poorly efficient and cumbersome and conventional molecular imprinted polymer itself of active Chinese drug component screening
The shortcomings that, the invention provides a kind of nNOS-PSD-95 uncoupler imprint surface polymer based on magnetic mesoporous molecular sieve
Preparation method, it is intended to find activity significantly, the small anti-cerebral apoplexy drug candidate of toxic side effect, while be active ingredient of Chinese herbs
Specificity and high frequency zone new approaches and new method are provided.
Technical scheme：A kind of nNOS-PSD-95 uncoupler imprint surface polymer based on magnetic mesoporous molecular sieve
Preparation method, concretely comprise the following steps：A. the magnetic mesoporous molecular sieve of core shell structure is prepared：With solvent structure inorganic magnetic nanometer
Particle core, and tetraethyl orthosilicate and surfactant are added under magnetic stirring, products therefrom by acetone reflux or
Volume ratio is dispersed in as 1:20~1:It is stirred at room temperature in 200 hydrochloric acid-Alcohol system and removes unnecessary surfactant, most
Deionization is washed afterwards, vacuum drying, obtains the magnetic mesoporous silicon dioxide microsphere of core shell structure；B. to obtained magnetic mesoporous two
Silicon oxide microsphere carries out surface graft modification：By magnetic mesoporous silicon dioxide microsphere ultrasonic disperse in toluene solution, under stirring
Add the volume of methacryloxypropyl trimethoxy silane, methacryloxypropyl trimethoxy silane and toluene
Than for 1:10~3:10, lead to nitrogen deoxygenation, sealing, 65~120 DEG C of heating stirrings backflow 24h, obtain the magnetic after graft modification
Mesopore molecular sieve, then washed successively with toluene, methanol, Magnetic Isolation is standby after vacuum drying；C. prepare based on magnetic mesoporous point
The nNOS-PSD-95 uncoupler imprint surface polymer of son sieve：Template molecule ZL006 and function monomer are added into pore-foaming agent,
The mol ratio of template molecule and function monomer is 1:4~1:6, pore-foaming agent and template molecule Molar ratio are 100~250mL/
Mmol, 30 DEG C of stirring 4h, obtains solution one；Magnetic mesoporous silicon dioxide microsphere ultrasonic disperse after surface graft modification is in pore
Agent, solution two is obtained, it is rear to add crosslinking agent and initiator, work(by solution one and solution two by any uniformly mixing more lower than stirring
The mol ratio of energy monomer and crosslinking agent is 1:3~1:6, initiator amount is that template molecule, function monomer and crosslinking agent quality are total
The 3%~5% of amount, lead to nitrogen-sealed, heating stirring backflow；Reaction terminates rear Magnetic Isolation and removes supernatant, is scattered in volume again
Than for 9:1 methanol-glacial acetic acid mixed solution, it is placed in shaken cultivation case and vibrates washing repeatedly, until supernatant ultraviolet detection is not
Untill template molecule, again with methanol is washed till neutrality, is dried under vacuum to constant weight, obtains the nNOS- based on magnetic mesoporous molecular sieve
PSD-95 uncoupler imprint surface polymer.
The rate of addition of tetraethyl orthosilicate is that 2~30s mono- drips in above-mentioned steps A；Magnetic stirring rotating speed be 500~
1100rpm/min；The volume ratio of hydrochloric acid-ethanol is 1:200.
Methacryloxypropyl trimethoxy silane and the volume ratio of toluene are 1 in above-mentioned steps B:5；It is stirred at reflux
Temperature be 115 DEG C.
Function monomer described in above-mentioned steps C is acrylamide, methyl methacrylate, 4-vinylpridine or N,
N'- methylene-bisacrylamides.
Crosslinking agent described in above-mentioned steps C is ethylene glycol dimethacrylate or trimethylol propane trimethyl propylene
Acid esters.
Pore-foaming agent described in above-mentioned steps C is DMF, tetrahydrofuran, volume ratio 9:1 toluene-ethano
System or volume ratio 9:1 acetonitrile-ethanol system.
Initiator described in above-mentioned steps C is azodiisobutyronitrile.
The mol ratio of template molecule and function monomer is 1 in above-mentioned steps C:5, the mol ratio of function monomer and crosslinking agent is
1:5, pore-foaming agent and template molecule Molar ratio are 125mL/mmol, and initiator amount is template molecule, function monomer and friendship
Join the 5% of agent quality total amount.
Heating step when being heated to reflux in above-mentioned steps C is 50 DEG C of reaction 6h, 60 DEG C of reaction 24h, is finally warming up to 85
DEG C reaction 6h.
Beneficial effect：Chinese medicine system is huge, complicated component, various structures, interfering component are more, and the screening of its active component is low
Imitate and cumbersome, and be easy to lose micro active ingredient, the nNOS-PSD-95 based on magnetic mesoporous molecular sieve prepared by the present invention
Uncoupler imprint surface polymer monodispersity is good, and specific surface area is big, mesoporous regular, has excellent absorption and desorption
Attached dynamics, and polymer stabilisation, favorable reproducibility, to realize the selectivity of nNOS-PSD-95 uncouplers in Chinese medicine
Capture and high frequency zone provide may.Meanwhile be combined magnetic separation technique and dispersive solid-phase extraction, eliminate centrifugation, filtering
Etc. numerous and diverse operation, separating rate is accelerated, effectively shortens the time of screening compound, it is simple to operate, it is easily recycled, favorably
It is more environmentally-friendly in recycling.
Brief description of the drawings
Fig. 1 is the technology for preparing the nNOS-PSD-95 uncoupler imprint surface polymer based on magnetic mesoporous molecular sieve
Route map.
Fig. 2 is the transmission electron microscope picture of magnetic mesoporous molecular sieve.
Fig. 3 is the ZL006 absorption of the nNOS-PSD-95 uncoupler imprint surface polymer based on magnetic mesoporous molecular sieve
Curve map, left figure are Static Adsorption isollaothermic chart (a：MIP, b：NIP), right figure is curve of adsorption kinetics figure.
Fig. 4 is that the desorption of the nNOS-PSD-95 uncoupler imprint surface polymer based on magnetic mesoporous molecular sieve is moved
Force diagram figure and regenerative adsorption column diagram.
Fig. 5 is even based on magnetic separation technique and nNOS-PSD-95 solutions in dispersive solid-phase extraction combination System For Screening Chinese medicine
Join the Technology Roadmap of agent.
Embodiment
The present invention is described in further detail below in conjunction with accompanying drawing embodiment.
Iron(III) chloride hexahydrate (FeCl3·6H2O)
Anhydrous sodium acetate (NaAc)
Tetraethyl orthosilicate (TEOS)
Cetyl trimethylammonium bromide (CTAB)
Methacryloxypropyl trimethoxy silane (MPS)
Acrylamide (AM)
Methyl methacrylate (MMA)
4-vinylpridine (4-VP)
N, N'- methylene-bisacrylamide (MBA)
Trimethylol-propane trimethacrylate (TRIM)
Ethylene glycol dimethacrylate (EGDMA)
DMF (DMF)
Tetrahydrofuran (THF)
Azodiisobutyronitrile (AIBN)
Embodiment 1：
(1) weighs 2.7gFeCl3·6H2O and 7.2gNaAc, magnetic stirring are dissolved in 100mL ethylene glycol in uniformly yellow
Color solution, tetrafluoroethene autoclave, 200 DEG C of standing 8h are transferred to, room temperature is cooled down, and absolute ethyl alcohol is washed 6 times, Magnetic Isolation, 45 DEG C
Constant weight is dried under vacuum to, obtains Fe3O4Powder.
(2) weighs obtained Fe3O4Powder 0.1g ultrasonic disperses add 20mL deionized waters, the dense ammonia of 1mL in 80mL ethanol
Water, 0.1gTEOS is added dropwise into solution under magnetic agitation, 6h is stirred at room temperature, ethanol, deionization washing, is scattered in 60mL second again
Alcohol, 80mL deionized waters, 1g concentrated ammonia liquors mixed solution in, add 0.3gCTAB, 30min be stirred at room temperature, it is rear to be added dropwise
0.4gTEOS, continue to stir 6h, rotating speed 500rpm, TEOS rate of addition are to drip per 2s mono-, and rear product of collecting is dispersed in 1mL
In HCl and 100mL alcohol mixed solutions, it is stirred at room temperature two days, Magnetic Isolation, 45 DEG C are dried under vacuum to constant weight, obtain magnetic mesoporous
Molecular sieve powder.
(3) weighs magnetic mesoporous molecular sieve powder ultrasonic disperse made from 0.1g in 50mL toluene solutions, adds 5mL
MPS, logical nitrogen are more than 10min, seal, rotating speed 1000rpm, and 24h is stirred at reflux at 65 DEG C, obtained modified magnetic mesoporous
Molecular sieve, washed successively with toluene, methanol, remove unreacted MPS, Magnetic Isolation, 45 DEG C are dried under vacuum to constant weight, standby.
(4) takes 0.3mmol ZL006, and in 1.5mmolMMA, ultrasonic disperse 25mL DMF, 30 DEG C of stirring 4h, rotating speed is
300rpm, obtains solution one, separately weighs the above-mentioned modified magnetic mesoporous molecular sieve powders of 0.1g and is dispersed in 25mL DMF, surpasses
Sound 30min, solution two is obtained, solution one, solution two are mixed, be stirring evenly and then adding into 6mmol EGDMA, 43.1mg AIBN, led to
Nitrogen is more than 10min, sealing, heating stirring backflow, 50 DEG C of reaction 6h, 60 DEG C of reaction 24h, is finally warming up to 85 DEG C of reaction 6h.
(5) reactions terminate rear Magnetic Isolation and remove supernatant, and it is 9 to be scattered in volume ratio again:1 methanol-glacial acetic acid mixing is molten
Liquid, it is placed in shaken cultivation case and vibrates washing repeatedly, untill supernatant ultraviolet detection is less than template molecule, again with methanol is washed till
Neutrality, 45 DEG C are dried under vacuum to constant weight, obtain the nNOS-PSD-95 uncoupler imprint surfaces based on magnetic mesoporous molecular sieve and gather
Compound (MIP-1).
The preparation process of non-imprinted polymer (NIP-1), in addition to template molecule is not added in building-up process, remaining step
It is rapid identical with MIP-1.
Embodiment 2:
(1) weighs 2.7g FeCl3·6H2O and 7.2gNaAc, magnetic stirring are dissolved in 100mL ethylene glycol in uniformly yellow
Color solution, tetrafluoroethene autoclave, 200 DEG C of standing 8h are transferred to, room temperature is cooled down, and absolute ethyl alcohol is washed 6 times, Magnetic Isolation, 45 DEG C
Constant weight is dried under vacuum to, obtains Fe3O4Powder.
(2) weighs obtained Fe3O4Powder 0.1g ultrasonic disperses add 20mL deionized waters, the dense ammonia of 1mL in 80mL ethanol
Water, 0.1gTEOS is added dropwise into solution under magnetic agitation, 6h is stirred at room temperature, ethanol, deionization washing, is scattered in 60mL second again
Alcohol, 80mL deionized waters, 1g concentrated ammonia liquors mixed solution in, add 0.3gCTAB, 30min be stirred at room temperature, it is rear to be added dropwise
0.4gTEOS, continue to stir 6h, rotating speed 600rpm, TEOS rate of addition are to drip per 10s mono-, and rear product of collecting is scattered in 60mL
In acetone, 80 DEG C are flowed back two days, are repeated twice backflow, Magnetic Isolation, 45 DEG C are dried under vacuum to constant weight, obtain magnetic mesoporous molecular sieve
Powder.
(3) weighs magnetic mesoporous molecular sieve powder ultrasonic disperse made from 0.1g in 50mL toluene solutions, adds 6mL
MPS, logical nitrogen are more than 10min, seal, rotating speed 1000rpm, and 24h is stirred at reflux at 75 DEG C, obtained modified magnetic mesoporous
Molecular sieve, washed successively with toluene, methanol, remove unreacted MPS, Magnetic Isolation, 45 DEG C are dried under vacuum to constant weight, standby.
(4) takes 0.5mmol ZL006, and in 2mmol4-VP, ultrasonic disperse 25mL THF, 30 DEG C of stirring 4h, rotating speed is
300rpm, obtains solution one, separately weighs the above-mentioned modified magnetic mesoporous molecular sieve powders of 0.1g and is dispersed in 25mL THF, surpasses
Sound 30min, solution two is obtained, solution one, solution two is mixed, be stirring evenly and then adding into 6mmol EGDMA, 62.54mg AIBN,
Logical nitrogen is more than 10min, seals, heating stirring backflow, 50 DEG C of reaction 6h, 60 DEG C of reaction 24h, is finally warming up to 85 DEG C of reactions
6h。
(5) reactions terminate rear Magnetic Isolation and remove supernatant, and it is 9 to be scattered in volume ratio again:1 methanol-glacial acetic acid mixing is molten
Liquid, it is placed in shaken cultivation case and vibrates washing repeatedly, untill supernatant ultraviolet detection is less than template molecule, again with methanol is washed till
Neutrality, 45 DEG C are dried under vacuum to constant weight, obtain the nNOS-PSD-95 uncoupler imprint surfaces based on magnetic mesoporous molecular sieve and gather
Compound.(MIP-2)
The preparation process of non-imprinted polymer (NIP-2), in addition to template molecule is not added in building-up process, remaining step
It is rapid identical with MIP-2.
Embodiment 3:
(1) weighs 2.7g FeCl3·6H2O and 7.2gNaAc, magnetic stirring are dissolved in 100mL ethylene glycol in uniformly yellow
Color solution, tetrafluoroethene autoclave, 200 DEG C of standing 8h are transferred to, room temperature is cooled down, and absolute ethyl alcohol is washed 6 times, Magnetic Isolation, 45 DEG C
Constant weight is dried under vacuum to, obtains Fe3O4Powder.
(2) weighs obtained Fe3O4Powder 0.1g ultrasonic disperses add 20mL deionized waters, the dense ammonia of 1mL in 80mL ethanol
Water, 0.1gTEOS is added dropwise into solution under magnetic agitation, 6h is stirred at room temperature, ethanol, deionization washing, is scattered in 60mL second again
Alcohol, 80mL deionized waters, 1g concentrated ammonia liquors mixed solution in, add 0.3gCTAB, 30min be stirred at room temperature, it is rear to be added dropwise
0.4gTEOS, continue to stir 6h, rotating speed 700rpm, TEOS rate of addition are to drip per 15s mono-, and rear product of collecting is dispersed in
In 3mLHCl and 100mL alcohol mixed solutions, it is stirred at room temperature two days, Magnetic Isolation, 45 DEG C are dried under vacuum to constant weight, obtain magnetic Jie
Porous molecular sieve powder.
(3) weighs magnetic mesoporous molecular sieve powder ultrasonic disperse made from 0.1g in 50mL toluene solutions, adds 7mL
MPS, logical nitrogen are more than 10min, seal, rotating speed 1000rpm, are stirred at reflux 24h at 100 DEG C, modified magnetic Jie is made
Porous molecular sieve, washed successively with toluene, methanol, remove unreacted MPS, Magnetic Isolation, 45 DEG C are dried under vacuum to constant weight, standby
With.
(4) takes 0.2mmol ZL006,1.2mmolMBA, ultrasonic disperse 25mL toluene-ethanos (9:1, v/v) in, 30 DEG C
4h, rotating speed 300rpm are stirred, solution one is obtained, separately weighs the above-mentioned modified magnetic mesoporous molecular sieve powders of 0.1g and be dispersed in
25mL toluene-ethano (9：1, v/v) in F, ultrasonic 30min, solution two is obtained, solution one, solution two is mixed, after stirring
7.2mmolTrim, 134.35mg AIBN are added, logical nitrogen is more than 10min, seals, heating stirring backflow, and 50 DEG C are reacted 6h, and 60
DEG C reaction 24h, be finally warming up to 85 DEG C reaction 6h.
(5) reactions terminate rear Magnetic Isolation and remove supernatant, and it is 9 to be scattered in volume ratio again:1 methanol-glacial acetic acid mixing is molten
Liquid, it is placed in shaken cultivation case and vibrates washing repeatedly, untill supernatant ultraviolet detection is less than template molecule, again with methanol is washed till
Neutrality, 45 DEG C are dried under vacuum to constant weight, obtain the nNOS-PSD-95 uncoupler imprint surfaces based on magnetic mesoporous molecular sieve and gather
Compound.(MIP-3)
The preparation process of non-imprinted polymer (NIP-3), in addition to template molecule is not added in building-up process, remaining step
It is rapid identical with MIP-3.
Embodiment 4：
(1) weighs 2.7g FeCl3·6H2O and 7.2gNaAc, magnetic stirring are dissolved in 100mL ethylene glycol in uniformly yellow
Color solution, tetrafluoroethene autoclave, 200 DEG C of standing 8h are transferred to, room temperature is cooled down, and absolute ethyl alcohol is washed 6 times, Magnetic Isolation, 45 DEG C
Constant weight is dried under vacuum to, obtains Fe3O4Powder.
(2) weighs obtained Fe3O4Powder 0.1g ultrasonic disperses add 20mL deionized waters, the dense ammonia of 1mL in 80mL ethanol
Water, 0.1gTEOS is added dropwise into solution under magnetic agitation, 6h is stirred at room temperature, ethanol, deionization washing, is scattered in 60mL second again
Alcohol, 80mL deionized waters, 1g concentrated ammonia liquors mixed solution in, add 0.3gCTAB, 30min be stirred at room temperature, it is rear to be added dropwise
0.4gTEOS, continue to stir 6h, rotating speed 1000rpm, TEOS rate of addition are to drip per 20s mono-, and rear product of collecting is dispersed in
In 0.5mLHCl and 100mL alcohol mixed solutions, it is stirred at room temperature two days, Magnetic Isolation, 45 DEG C are dried under vacuum to constant weight, obtain magnetic
Mesopore molecular sieve powder.
(3) weighs magnetic mesoporous molecular sieve powder ultrasonic disperse made from 0.1g in 50mL toluene solutions, adds 10mL
MPS, logical nitrogen are more than 10min, seal, rotating speed 1000rpm, are stirred at reflux 24h at 115 DEG C, modified magnetic Jie is made
Porous molecular sieve, washed successively with toluene, methanol, remove unreacted MPS, Magnetic Isolation, 45 DEG C are dried under vacuum to constant weight, standby
With.
(4) takes 0.4mmol ZL006,2mmolAM, ultrasonic disperse 25mL acetonitrile-ethanols (9:1, v/v) in, 30 DEG C of stirrings
4h, rotating speed 300rpm, obtain solution one, separately weigh the above-mentioned modified magnetic mesoporous molecular sieve powders of 0.1g and are dispersed in 25mL second
Nitrile-ethanol (9：1, v/v) in, ultrasonic 30min, solution two is obtained, solution one, solution two is mixed, are stirring evenly and then adding into
10mmol EGDMA, 112.77mg AIBN, logical nitrogen are more than 10min, seal, heating stirring backflow, and 50 DEG C are reacted 6h, 60 DEG C
24h is reacted, is finally warming up to 85 DEG C of reaction 6h.
(5) reactions terminate rear Magnetic Isolation and remove supernatant, and it is 9 to be scattered in volume ratio again:1 methanol-glacial acetic acid mixing is molten
Liquid, it is placed in shaken cultivation case and vibrates washing repeatedly, untill supernatant ultraviolet detection is less than template molecule, again with methanol is washed till
Neutrality, 45 DEG C are dried under vacuum to constant weight, obtain the nNOS-PSD-95 uncoupler imprint surfaces based on magnetic mesoporous molecular sieve and gather
Compound.(MIP-4)
The preparation process of non-imprinted polymer (NIP-4), in addition to template molecule is not added in building-up process, remaining step
It is rapid identical with MIP-4.
Embodiment 5：
(1) weighs 2.7gFeCl3·6H2O and 7.2gNaAc, magnetic stirring are dissolved in 100mL ethylene glycol in uniformly yellow
Color solution, tetrafluoroethene autoclave, 200 DEG C of standing 8h are transferred to, room temperature is cooled down, and absolute ethyl alcohol is washed 6 times, Magnetic Isolation, 45 DEG C
Constant weight is dried under vacuum to, obtains Fe3O4Powder.
(2) weighs obtained Fe3O4Powder 0.1g ultrasonic disperses add 20mL deionized waters, the dense ammonia of 1mL in 80mL ethanol
Water, 0.1gTEOS is added dropwise into solution under magnetic agitation, 6h is stirred at room temperature, ethanol, deionization washing, is scattered in 60mL second again
Alcohol, 80mL deionized waters, 1g concentrated ammonia liquors mixed solution in, add 0.3gCTAB, 30min be stirred at room temperature, it is rear to be added dropwise
0.4gTEOS, continue to stir 6h, rotating speed 1100rpm, TEOS rate of addition are to drip per 30s mono-, and rear product of collecting is dispersed in
In 5mLHCl and 100mL alcohol mixed solutions, it is stirred at room temperature two days, Magnetic Isolation, 45 DEG C are dried under vacuum to constant weight, obtain magnetic Jie
Porous molecular sieve powder.
(3) weighs magnetic mesoporous molecular sieve powder ultrasonic disperse made from 0.1g in 50mL toluene solutions, adds 15mL
MPS, logical nitrogen are more than 10min, seal, rotating speed 1000rpm, are stirred at reflux 24h at 120 DEG C, modified magnetic Jie is made
Porous molecular sieve, washed successively with toluene, methanol, remove unreacted MPS, Magnetic Isolation, 45 DEG C are dried under vacuum to constant weight, standby
With.
(4) takes 0.3mmol ZL006,1.8mmolMMA, ultrasonic disperse 25mL acetonitrile-ethanols (9:1, v/v) in, 30 DEG C
4h, rotating speed 300rpm are stirred, solution one is obtained, separately weighs the above-mentioned modified magnetic mesoporous molecular sieve powders of 0.1g and be dispersed in
25mL acetonitrile-ethanols (9：1, v/v) in, ultrasonic 30min, solution two is obtained, solution one, two is mixed, is stirring evenly and then adding into
7.2mmol Trim, 81.45mg AIBN, logical nitrogen are more than 10min, sealed, heating stirring backflow, and 50 DEG C of reaction 6h, 60 DEG C anti-
24h is answered, is finally warming up to 85 DEG C of reaction 6h.
(5) reactions terminate rear Magnetic Isolation and remove supernatant, and it is 9 to be scattered in volume ratio again:1 methanol-glacial acetic acid mixing is molten
Liquid, it is placed in shaken cultivation case and vibrates washing repeatedly, untill supernatant ultraviolet detection is less than template molecule, again with methanol is washed till
Neutrality, 45 DEG C are dried under vacuum to constant weight, obtain the nNOS-PSD-95 uncoupler imprint surfaces based on magnetic mesoporous molecular sieve and gather
Compound.(MIP-5)
The preparation process of non-imprinted polymer (NIP-5), in addition to template molecule is not added in building-up process, remaining step
It is rapid identical with MIP-5.
Testing example：
Testing example 1：Optimization of synthesis
MIP made from above-described embodiment and each 1 part of NIP (20.0mg) are weighed, is placed in 15mL triangular flasks, is separately added into
2.5mmol/L ZL006 solution 5mL, ultrasonic disperse, rocked at room temperature 2h, take supernatant, are filtered with 0.22 μm of nylon membrane, fixed
Amount dilution, spectrophotometry instrument ZL006 solution concentrations before and after measure absorption at 290nm.Calculated according to formula (1)
Equilibrium adsorption capacity Q, marking factor IF is calculated according to formula (2), operation repetitive is three times.
Q=V (C0-Ce)/W (1)
In formula：C0And CeThe respectively initial concentration of template molecule and equilibrium concentration (mmol/L)；V is the body of adsorbent solution
Product (mL)；W is the quality (g) of imprinted polymer.
IF=QMIP/QNIP (2)
In formula：QMIPAnd QNIPEquilibrium adsorption capacities (μm ol/g) of the respectively MIP and NIP to ZL006.
MIP made from embodiment 4 shows higher adsorbance and preferably absorption to ZL006 as can be seen from Table 1
Selectivity.
The synthesis technique of nNOS-PSD-95 uncoupler imprint surface polymer of the table 1 based on magnetic mesoporous molecular sieve is excellent
Change table
| QMIPs(μmol g-1) | IF | |
| MIP-1 | 93.7 | 1.59 |
| MIP-2 | 84.1 | 1.3 |
| MIP-3 | 58.3 | 1.27 |
| MIP-4 | 106.41 | 1.92 |
| MIP-5 | 79.8 | 1.44 |
Take the nNOS-PSD-95 uncoupler imprint surfaces based on magnetic mesoporous molecular sieve synthesized in above-described embodiment 4
Polymer carries out following test experiments.
Testing example 2：Transmission electron microscope characterizes
Fig. 2 is the transmission electron microscope picture for the magnetic mesoporous molecular sieve that the present invention synthesizes, it is seen that its uniform particle diameter, monodispersity
It is good.
Testing example 3：Static Adsorption is tested
Weigh MIP and each 6 parts of NIP (20.0mg), be placed in 15mL triangular flasks, be separately added into 0.5,1.0,1.5,2.0,
2.5th, 3mmol/L ZL006 solution 5mL, ultrasonic disperse, rocked at room temperature 2h, take supernatant, are filtered with 0.22 μm of nylon membrane,
Quantitative dilution, spectrophotometry instrument ZL006 solution concentrations before and after measure absorption at 290nm.Calculated according to formula (1)
Go out equilibrium adsorption capacity Q, operation repetitive is three times.
From Fig. 3 (left side) as can be seen that MIP is significantly greater than NIP adsorbance to ZL006 adsorbance, show MIP pairs
ZL006 absorption is different from physical absorption, but a kind of selective absorption for having specific recognition site, this molecular recognition are special
Property come from the geometry selectivity in hydrogen bond action between the conjugated group of the polymer and the function base of template molecule and hole.
Testing example 4：Adsorption dynamics adsorption kinetics is tested
Precision weighs 9 parts of MIP (20.0mg), is placed in 15mL triangular flasks, is separately added into 2.5mmol/L ZL006 solution
5mL, ultrasonic disperse, rocked at room temperature, supernatant is taken in 2,5,10,15,20,25,30,35min respectively, with 0.22 μm of nylon
Membrane filtration mistake, quantitative dilution, spectrophotometry instrument ZL006 solution concentrations before and after measure absorption at 290nm, according to formula
(1) equilibrium adsorption capacity Q is calculated, operation repetitive is three times.
From Fig. 3 (right side) as can be seen that imprinted material has the faster rate of adsorption, absorption can be rapidly reached in 30min
Balance.And MIP time of equilibrium adsorption prepared by traditional polymerisation in bulk is generally 12~24h.Its reason is to use surface molecular
Its recognition site of the MIP of trace preparation is located at the uniform and thin imprinted layer of material surface, and accessibility is strong, and mass transfer velocity is fast, can
To be rapidly achieved adsorption equilibrium.
Testing example 5：Desorption dynamic test
Precision weighs 9 parts of MIP (20.0mg), is placed in 15mL triangular flasks, is separately added into 2.5mmol/L ZL006 solution
5mL, ultrasonic disperse, rocked at room temperature 30min, supernatant is removed, be separately added into volume ratio as 9:1 methanol-glacial acetic acid mixing is molten
Liquid 1mL, supernatant is taken after ultrasound 1,2,5,10,15,20,25,30,35min respectively, volume ratio 9 is used after nitrogen drying:1 acetonitrile-
Alcohol mixed solution redissolves, 0.22 μm of nylon membrane filtration, quantitative dilution, and spectrophotometry instrument determines suction at 290nm
Attached front and rear ZL006 solution concentrations, calculate equilibrium adsorption capacity Q and desorption efficiency of the polymer in the different desorption times, parallel behaviour
Make three times.
From Fig. 4 (left side) as can be seen that imprinted material has faster desorption speed, the basic desorptions of about 20min are complete.
Its reason be also due to recognition site material surface rule, arrange in an orderly manner.
Testing example 6：Stability and reusability experiment
Precision weighs 1 part of MIP (20.0mg), is placed in 15mL triangular flasks, adds 2.5mmol/L ZL006 solution 5mL,
Ultrasonic disperse, rocked at room temperature 30min, takes supernatant, is filtered with 0.22 μm of nylon membrane, quantitative dilution, UV-vis spectroscopy light
Spend instrument ZL006 solution concentrations before and after measure absorption at 290nm.Equilibrium adsorption capacity Q and adsorption rate are calculated, removes supernatant afterwards
Liquid, it is 9 to add volume ratio:Magnetic Isolation collected polymer after 1 methanol-glacial acetic acid mixed solution 1mL, ultrasonic 20min, vacuum
Dry.So repeat six times.
From Fig. 4 (right side) as can be seen that adsorption rate does not change significantly after using six times, illustrate prepared imprinting polymerization
Thing has preferable stability and reappearance, can be applied to nNOS-PSD- in Chinese medicine as the adsorbent of dispersive solid-phase extraction
The selectivity capture of 95 uncouplers and high frequency zone.
The foregoing examples are merely illustrative of the technical concept and features of the invention, its object is to allow the person skilled in the art to be
Present disclosure can be understood and implemented according to this, it is not intended to limit the scope of the present invention.It is all smart according to the present invention
The equivalent transformation or modification that refreshing essence is done, should all be included within the scope of the present invention.
Claims (9)
1. a kind of preparation method of the nNOS-PSD-95 uncoupler imprint surface polymer based on magnetic mesoporous molecular sieve, its
It is characterised by concretely comprising the following steps：
A. the magnetic mesoporous molecular sieve of core shell structure is prepared：
With solvent structure inorganic magnetic nano-particle core, and add tetraethyl orthosilicate under magnetic stirring and surface is lived
Property agent, products therefrom is by acetone reflux or is dispersed in volume ratio as 1:20~1:Room in 200 hydrochloric acid-Alcohol system
Temperature stirring removes unnecessary surfactant, last deionization washing, vacuum drying, obtains the magnetic mesoporous dioxy of core shell structure
SiClx microballoon；
B. surface graft modification is carried out to obtained magnetic mesoporous silicon dioxide microsphere：
By magnetic mesoporous silicon dioxide microsphere ultrasonic disperse in toluene solution, lower addition methacryloxypropyl three is stirred
The volume ratio of methoxy silane, methacryloxypropyl trimethoxy silane and toluene is 1:10~3:10, logical nitrogen removes
Oxygen, sealing, 65~120 DEG C of heating stirrings flow back 24h, obtain the magnetic mesoporous molecular sieve after graft modification, then successively with toluene,
Methanol washs, and Magnetic Isolation is standby after vacuum drying；
C. the nNOS-PSD-95 uncoupler imprint surface polymer based on magnetic mesoporous molecular sieve is prepared：
By template molecule ZL006 and function monomer addition pore-foaming agent, the mol ratio of template molecule and function monomer is 1:4~1:6,
Pore-foaming agent is 100~250mL/mmol with template molecule Molar ratio, 30 DEG C of stirring 4h, obtains solution one；Surface grafting changes
Property after magnetic mesoporous silicon dioxide microsphere ultrasonic disperse in pore-foaming agent, solution two is obtained, by solution one and solution two by any
The mol ratio of uniformly mixing more lower than stirring, rear addition crosslinking agent and initiator, function monomer and crosslinking agent is 1:3~1:6, trigger
Agent dosage is the 3%~5% of template molecule, function monomer and crosslinking agent quality total amount, leads to nitrogen-sealed, heating stirring backflow；Instead
Magnetic Isolation removes supernatant after should terminating, and is scattered in volume ratio again for 9:1 methanol-glacial acetic acid mixed solution, it is placed in vibration training
Foster case vibrates washing repeatedly, and untill supernatant ultraviolet detection is less than template molecule, again with methanol is washed till neutrality, vacuum drying
To constant weight, the nNOS-PSD-95 uncoupler imprint surface polymer based on magnetic mesoporous molecular sieve is obtained.
2. the nNOS-PSD-95 uncouplers imprint surface polymerization according to claim 1 based on magnetic mesoporous molecular sieve
The preparation method of thing, it is characterised in that the rate of addition of tetraethyl orthosilicate is that 2~30s mono- drips in step A；Magnetic stirring turns
Speed is 500~1100rpm/min；The volume ratio of hydrochloric acid-ethanol is 1:200.
3. the nNOS-PSD-95 uncouplers imprint surface polymerization according to claim 1 based on magnetic mesoporous molecular sieve
The preparation method of thing, it is characterised in that methacryloxypropyl trimethoxy silane and the volume ratio of toluene are in step B
1:5；The temperature being stirred at reflux is 115 DEG C.
4. the nNOS-PSD-95 uncouplers imprint surface polymerization according to claim 1 based on magnetic mesoporous molecular sieve
The preparation method of thing, it is characterised in that the function monomer described in step C is acrylamide, methyl methacrylate, 4- ethene
Yl pyridines or N, N'- methylene-bisacrylamide.
5. the nNOS-PSD-95 uncouplers imprint surface polymerization according to claim 1 based on magnetic mesoporous molecular sieve
The preparation method of thing, it is characterised in that the crosslinking agent described in step C is ethylene glycol dimethacrylate or trihydroxy methyl third
Alkane trimethyl acrylic ester.
6. the nNOS-PSD-95 uncouplers imprint surface polymerization according to claim 1 based on magnetic mesoporous molecular sieve
The preparation method of thing, it is characterised in that the pore-foaming agent described in step C is DMF, tetrahydrofuran, volume ratio
9:1 toluene-ethano system or volume ratio 9:1 acetonitrile-ethanol system.
7. the nNOS-PSD-95 uncouplers imprint surface polymerization according to claim 1 based on magnetic mesoporous molecular sieve
The preparation method of thing, it is characterised in that the initiator described in step C is azodiisobutyronitrile.
8. the nNOS-PSD-95 uncouplers imprint surface polymerization according to claim 1 based on magnetic mesoporous molecular sieve
The preparation method of thing, it is characterised in that the mol ratio of template molecule and function monomer is 1 in step C:5, function monomer is with being crosslinked
The mol ratio of agent is 1:5, pore-foaming agent and template molecule Molar ratio be 125mL/mmol, initiator amount be template molecule,
The 5% of function monomer and crosslinking agent quality total amount.
9. the nNOS-PSD-95 uncouplers imprint surface polymerization according to claim 1 based on magnetic mesoporous molecular sieve
The preparation method of thing, it is characterised in that heating step when being heated to reflux in step C is 50 DEG C of reaction 6h, and 60 DEG C are reacted 24h,
Finally it is warming up to 85 DEG C of reaction 6h.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108283603A (en) * | 2018-04-02 | 2018-07-17 | 吴伟华 | A kind of preparation method of labour protection cold cream |
| CN109350747A (en) * | 2018-10-31 | 2019-02-19 | 南京医科大学 | A kind of ZL006 cyclohexyl polymer nanocomposite delivery system and preparation method thereof |
| CN110180603A (en) * | 2019-05-31 | 2019-08-30 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of preparation method and products thereof of porous amino-acid modified molecular sieve |
| CN110498751A (en) * | 2019-08-15 | 2019-11-26 | 南京医科大学 | A kind of imprinted templates molecule and its preparation method and application |
| CN112300347A (en) * | 2020-10-19 | 2021-02-02 | 江苏大学 | Preparation method and application of magnetic ferroferric oxide nanoparticle-based photoresponse imprinted material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101817908A (en) * | 2010-02-04 | 2010-09-01 | 南京医科大学 | Preparation method of molecular imprinting polymer of PSD-95/nNOS uncoupler |
| CN102127182A (en) * | 2010-12-23 | 2011-07-20 | 南京医科大学 | Method for preparing magnetic molecule mark polymer for detecting PDE-5 inhibitor |
| CN102964542A (en) * | 2012-12-10 | 2013-03-13 | 天津工业大学 | RAFT (Reversible addition-fragmentation chain transfer) polymerization preparation method of magnetic mesoporous molecular imprinted hybrid silicon spheres |
| CN103570871A (en) * | 2013-10-21 | 2014-02-12 | 南京医科大学 | Mesoporous molecular sieve SBA-15 composite nano surface imprinted polymer and preparation method thereof |
| CN104275155A (en) * | 2014-10-28 | 2015-01-14 | 武汉大学 | Preparation method of novel cadmium ion imprinting magnetic mesoporous silica gel solid-phase extracting agent as well as application of preparation method |
-
2017
- 2017-06-21 CN CN201710474123.2A patent/CN107353372B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101817908A (en) * | 2010-02-04 | 2010-09-01 | 南京医科大学 | Preparation method of molecular imprinting polymer of PSD-95/nNOS uncoupler |
| CN102127182A (en) * | 2010-12-23 | 2011-07-20 | 南京医科大学 | Method for preparing magnetic molecule mark polymer for detecting PDE-5 inhibitor |
| CN102964542A (en) * | 2012-12-10 | 2013-03-13 | 天津工业大学 | RAFT (Reversible addition-fragmentation chain transfer) polymerization preparation method of magnetic mesoporous molecular imprinted hybrid silicon spheres |
| CN103570871A (en) * | 2013-10-21 | 2014-02-12 | 南京医科大学 | Mesoporous molecular sieve SBA-15 composite nano surface imprinted polymer and preparation method thereof |
| CN104275155A (en) * | 2014-10-28 | 2015-01-14 | 武汉大学 | Preparation method of novel cadmium ion imprinting magnetic mesoporous silica gel solid-phase extracting agent as well as application of preparation method |
Non-Patent Citations (1)
| Title |
|---|
| WANG YONGWEI等: "Employment of Molecularly Imprinted Polymers to High-Throughput Screen nNOS-PSD-95 Interruptions: Structure and Dynamics Investigations on Monomer-Template Complexation", 《CHEMPHYSCHEM》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108283603A (en) * | 2018-04-02 | 2018-07-17 | 吴伟华 | A kind of preparation method of labour protection cold cream |
| CN109350747A (en) * | 2018-10-31 | 2019-02-19 | 南京医科大学 | A kind of ZL006 cyclohexyl polymer nanocomposite delivery system and preparation method thereof |
| CN109350747B (en) * | 2018-10-31 | 2022-03-01 | 南京医科大学 | ZL006 cyclohexyl polymer nano drug delivery system and preparation method thereof |
| CN110180603A (en) * | 2019-05-31 | 2019-08-30 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of preparation method and products thereof of porous amino-acid modified molecular sieve |
| CN110180603B (en) * | 2019-05-31 | 2021-12-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of porous amino acid modified molecular sieve and product thereof |
| CN110498751A (en) * | 2019-08-15 | 2019-11-26 | 南京医科大学 | A kind of imprinted templates molecule and its preparation method and application |
| CN110498751B (en) * | 2019-08-15 | 2021-10-08 | 南京医科大学 | Imprinted template molecule and preparation method and application thereof |
| CN112300347A (en) * | 2020-10-19 | 2021-02-02 | 江苏大学 | Preparation method and application of magnetic ferroferric oxide nanoparticle-based photoresponse imprinted material |
| CN112300347B (en) * | 2020-10-19 | 2022-05-20 | 江苏大学 | Preparation method and application of magnetic ferroferric oxide nanoparticle-based photoresponse imprinted material |
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