CN109046278A - A kind of preparation method and application of the hollow micro- shell of gang form molecularly imprinted polymer - Google Patents
A kind of preparation method and application of the hollow micro- shell of gang form molecularly imprinted polymer Download PDFInfo
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- CN109046278A CN109046278A CN201810741765.9A CN201810741765A CN109046278A CN 109046278 A CN109046278 A CN 109046278A CN 201810741765 A CN201810741765 A CN 201810741765A CN 109046278 A CN109046278 A CN 109046278A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
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Abstract
The invention discloses preparation methods and application that a kind of pair of sulfanilamide (SN) and quinolone antibiotics have the hollow micro- shell of gang form molecularly imprinted polymer of selective absorption effect.The preparation method of micro- shell includes the following steps: to prepare polystyrene nanoparticle, prepares pre-assembled solution, prepares molecular engram nanosphere, preparing hollow polymer material and removing template molecule.The hollow micro- shell of gang form molecularly imprinted polymer prepared by the present invention not only has many advantages, such as that molecularly imprinted polymer is selectively good, is compared to other kinds of molecularly imprinted polymer also and has that adsorption capacity is big, the rate of adsorption is fast, applied widely.The preparation method of hollow gang form molecular engram material provided by the invention, not only can solve the existing bottleneck problem of molecular engram material, can also significantly widen the selective absorption range of hollow molecules imprinted material, to widen the application range of molecular engram material.
Description
Technical field
The invention belongs to polymeric material fields, and in particular to a kind of to have selective absorption performance to two class compounds
The preparation method and application of the hollow micro- shell of gang form molecularly imprinted polymer.
Background technique
Molecular imprinting technology is the technology for the molecularly imprinted polymer material that synthesis has molecular recognition function, molecular engram
Principle be that will form multiple action point when template molecule and polymer material monomer contact, by polymerization process by this work
With memorizing, after template molecule removes, the tool to match with template molecule steric configuration is formed in polymer material
There is the hole of multiple action point, such hole there will be Selective recognition characteristic to template molecule and the like.Therefore, divide
Sub- imprinted polymer has good selectivity the advantages that stability with height, is widely used in chromatographic isolation, solid phase extraction
Take, trace analysis, clinical medicine analysis etc. fields.
Hollow molecules imprinted material can solve the removal of molecular engram material template since adsorption capacity is big to a certain extent
Slowly, adsorption capacity is low and the disadvantages of mass transfer is slow, is applied in complex matrices sample extraction.But hollow molecules imprinted material
The characteristics of being only capable of one class formation of selective absorption similar compound, significantly limit hollow molecules imprinted material applies model
It encloses.Therefore, develop the molecular engram material of highly selective, high applicability and applied and had in the extraction of complex matrices sample
It is of great significance.
Summary of the invention
To solve the deficiencies in the prior art, the present invention provides a kind of hollow gang form molecularly imprinted polymers
The preparation method and application of micro- shell use two class compounds as template molecule, can significantly widen hollow molecules imprinted material
Selective absorption range, to widen the application range of molecular engram material.
To achieve the above object, the preparation of the hollow micro- shell material of gang form molecularly imprinted polymer of the present invention uses hard mold
Plate method, after the surface of polystyrene nanoparticle prepares gang form molecular engram microsphere, using methylene chloride by polyphenyl second
Alkene nanosphere removes, and obtains the hollow micro- shell of gang form molecularly imprinted polymer.
Technical solution is as follows:
A kind of preparation method of the hollow micro- shell of gang form molecularly imprinted polymer, includes the following steps:
S1, it prepares polystyrene nanoparticle: styrene, acrylic acid being dispersed in sodium bicarbonate aqueous solution, in nitrogen
Under protection, initiator ammonium sulfate is added by polymerization reaction and obtains polystyrene nanoparticle；
S2, pre-assembled solution is prepared: using sulphadiazine and Ciprofloxacin as template, using methacrylic acid as function monomer,
It disperses template and function monomer in dimethyl sulfoxide and dissolves, obtain pre-assembled solution；
S3, it prepares molecular engram nanosphere: the step S1 polystyrene nanoparticle prepared is dispersed in 12
In alkanoic acid aqueous sodium persulfate solution, the pre-assembled solution, cross-linker divinylbenzene and initiator for sequentially adding step S2 preparation are even
Two isobutyl cyanogen of nitrogen obtains molecular engram nanosphere by polymerization reaction；
S4, prepare hollow polymer material: molecular engram nanosphere prepared by step S3 removes polystyrene, obtains
Empty polymer material；
S5, removing template molecule: using soxhlet extraction method, utilizes the hollow of acetic acid methanol solution removal step S4 preparation
Template molecule sulphadiazine and Ciprofloxacin in polymer material obtain the hollow micro- shell of gang form molecularly imprinted polymer.
Under preferred embodiment, polystyrene nanoparticle described in step S1 the preparation method comprises the following steps: concentration be 1.0~2.0mg/
The sodium bicarbonate aqueous solution of mL is passed through nitrogen, and heating water bath sequentially adds acrylic acid, styrene and persulfuric acid to after 55~65 DEG C
Ammonium, under the mechanical stirring of 350~450rmp, 15~25h of polymerization reaction at a temperature of 68~72 DEG C；It uses at room temperature
8000~10000rpm is centrifuged 5~10min and removes supernatant liquor, obtains polystyrene nanoparticle；Use ethanol washing polyphenyl
It is ethylene nanoparticle 3~5 times, spare after drying to constant weight at 40~60 DEG C；1.0~2.0mg/mL sodium bicarbonate is molten
The weight ratio of liquid, acrylic acid, styrene, ammonium persulfate additive amount are as follows: (80~120): (0.5~1.5): (4.0~6.0):
(0.05~0.1).
Under preferred embodiment, prepared described in step S2 pre-assembled solution the preparation method comprises the following steps: by molar ratio are as follows: 1:1:(8~
12) sulphadiazine (template molecule), Ciprofloxacin (template molecule) and methacrylic acid (function monomer) is added in beaker, uses
The concentration that dimethyl sulfoxide is diluted to sulphadiazine is 25~50 μm of ol/g, and 20~25min of ultrasound under 500~800W power is obtained
Pre-assembled solution.
Under preferred embodiment, the method for molecular engram nanosphere is prepared described in step S3 are as follows: the polyphenyl for preparing step S1
Ethylene nanoparticle, is dispersed in the lauryl sodium sulfate aqueous solution of 0.2~0.3mg/mL, 250~350rpm's
It stirs emulsified 20~28 hours；The pre-assembled solution of step S2 preparation is added, under the stirring of 250~350rpm, continues cream
Change 20~28h；Then, cross-linker divinylbenzene and initiator azo-bis-isobutyl cyanide, initiated polymerization: 40~45 DEG C is added
Reaction 6~10 hours, 55~65 DEG C are reacted 18~25 hours, and 75~80 DEG C are reacted 1~3 hour；Reaction system is adopted at room temperature
It is centrifuged 10min with 3500~4500rpm, removes supernatant liquor, sediment cleans 3~4 removing impurity with ethyl alcohol, 50~60
Drying to constant weight at DEG C, obtains molecular engram nanosphere；The polystyrene nanoparticle, 0.2~0.3g/mL dodecyl sulphur
Acid sodium aqueous solution, pre-assembled solution, divinylbenzene, azo-bis-isobutyl cyanide additive amount weight ratio be (0.3~0.5): (80~
150): (10~25): (3~9): (0.05~0.10).
Under preferred embodiment, the method for hollow polymer material is prepared described in step S4 are as follows: the molecule for preparing step S3 prints
Methylene chloride, 18~22 DEG C of constant temperature, 140~160 times/min concussion 20~remove molecular engram nanometer for 24 hours is added in mark nanosphere
Polystyrene nanoparticle in microballoon, gained are precipitated as hollow polymer material；The molecular engram nanosphere and dichloro
The weight ratio of methane additive amount is (0.4~0.6): (30~50).
Under preferred embodiment, the method for template molecule is removed described in step S5 are as follows: utilize soxhlet extraction, be using volume ratio
The acetic acid methanol solution of 1:3~1:5 is solvent, the mould in hollow polymer material that at 68~72 DEG C prepared by extraction step S4
Plate molecule；The polymer for removing template molecule is washed into neutrality with deionized water, is obtained after drying to constant weight at 55~60 DEG C
The hollow micro- shell of gang form molecularly imprinted polymer；The volume ratio is that 1:3~1:5 acetic acid methanol solution and hollow polymer make
The weight ratio of dosage is (100~150): (1~2).
It is another object of the present invention to provide the hollow micro- shells of gang form molecularly imprinted polymer in enrichment sulfamido
Application in antibiotic and/or quinolone antibiotics, the enrichment refer to hollow gang form molecularly imprinted polymer is micro-
Shell adsorbs sulfa antibiotics and/or quinolone antibiotics as solid-phase adsorbent
Under preferred embodiment, the sulfa antibiotics include sulphadiazine, sulfamethyldiazine, 5-methoxysulfadiazine,
Daimeton, sulfamethoxazole, madribon, sulfanilamide (SN) quinoline dislike one of woods or a variety of.
Under preferred embodiment, the quinolone antibiotics include: Ciprofloxacin, lavo-ofloxacin, Lomefloxacin, En Nuosha
One of star is a variety of.
The beneficial effects of the present invention are:
The present invention is had the advantage that using the hollow micro- shell of gang form molecularly imprinted polymer prepared by hard template method
(1) adsorption capacity is big: bigger than other molecularly imprinted polymer adsorption capacities；
(2) rate of adsorption is fast: faster than the other types molecularly imprinted polymer rate of adsorption；
(3) selectivity is good: absorption of the hollow micro- shell of gang form molecularly imprinted polymer prepared by the present invention for template
With selectivity；
(4) it can be achieved selectively to inhale to two class compounds, including while sulfa antibiotics and quinolone antibiotics
It is attached.
Detailed description of the invention
Fig. 1 is the selective absorption result of h-MIMs and h-NIMs for sulfanilamide (SN) and quinolone antibiotics；
Fig. 2 is dynamic adsorption result of the h-MIMs for sulfanilamide (SN) and quinolone antibiotics.
Specific embodiment
Below by specific implementation example, the present invention will be further described.
Unless otherwise specified, the organic solvent concentration that the present invention uses is 100%
A kind of preparation method of the hollow micro- shell of gang form molecularly imprinted polymer, comprising the following steps:
S1, polystyrene nanoparticle is prepared: firstly, being passed through in the sodium bicarbonate aqueous solution that concentration is 1~2mg/mL
Nitrogen, heating water bath sequentially add acrylic acid, styrene and ammonium persulfate, so that sodium bicarbonate is water-soluble to after 55 DEG C~65 DEG C
The weight ratio of liquid, acrylic acid, styrene, ammonium persulfate are as follows: (80~120): (0.5~1.5): (4.0~6.0): (0.05~
0.1).Reaction system is under the mechanical stirring of 350~450rmp, 15~25h of polymerization reaction at a temperature of 68~72 DEG C, in room temperature item
5~10min is centrifuged using 8000~10000rpm under part and removes supernatant liquor, obtains polystyrene nanoparticle；Use ethyl alcohol
Washing polystyrene nanoparticle 3~5 times, it is spare after drying to constant weight at 40~60 DEG C；
S2, pre-assembled solution is prepared: using sulphadiazine and Ciprofloxacin as template molecule, using methacrylic acid as function list
Body；Sulphadiazine, Ciprofloxacin, methacrylic acid are weighed respectively in beaker, molar ratio are as follows: 1:1:(8~12), it is added two
First sulfoxide, makes 25~50 μm of ol/g of concentration of sulphadiazine and Ciprofloxacin, system under 500~800W power ultrasound 20~
25min obtains pre-assembled solution；
S3, molecular engram nanosphere is prepared: the polystyrene nanoparticle for taking step S1 to prepare, under ultrasonication
It is even to be dispersed in the lauryl sodium sulfate aqueous solution of 0.2~0.3g/mL, in the stirring of 250~350rpm emulsified 20~28
Hour；The pre-assembled solution of S2 preparation is added, continues 20~28h of emulsification under the stirring of 250~350rpm；Then, it is added and hands over
Join agent divinylbenzene and initiator azo-bis-isobutyl cyanide, wherein polystyrene nanoparticle, lauryl sodium sulfate aqueous solution,
Pre-assembled solution, divinylbenzene, azo-bis-isobutyl cyanide weight ratio be (0.3~0.5): (80~150): (10~25): (3
~9): (0.05~0.10)；Initiated polymerization, in order to improve the shape characteristic for preparing material, the temperature that polymerization reaction occurs
For temperature programming, condition are as follows: 40~45 DEG C are reacted 6~10 hours, and 55~65 DEG C are reacted 18~25 hours, 75~80 DEG C of reactions 1
~3 hours；After reaction system uses 3500~4500rpm to be centrifuged 10min at room temperature, supernatant liquor, sediment second are removed
Alcohol cleans 3~4 times and removes wherein impurity, spare after drying to constant weight at 50~60 DEG C；
S4, it prepares hollow polymer material: weighing molecular engram nanosphere made from step S3, methylene chloride is added,
18~22 DEG C of constant temperature, 140~160 times/min concussion 20~for 24 hours remove molecular engram nanosphere in pipe/polyhenylethylene nano grain
Son, gained are precipitated as hollow polymer material；Wherein, molecular engram nanosphere and the weight ratio of methylene chloride be (0.4~
0.6): (30~50).
S5, removing template molecule: utilizing soxhlet extraction, the use of the acetic acid methanol that volume ratio is 1:3~1:5 be solvent,
The template molecule in hollow polymer material that at 68~72 DEG C prepared by extraction step S4, to remove template molecule；Spend from
The polymer for removing template molecule is washed neutrality by sub- water, and hollow gang form point is obtained after drying to constant weight at 55~60 DEG C
The sub- micro- shell of imprinted polymer.Wherein, the weight ratio of acetic acid methanol solution and hollow polymer is (100~150): (1~2).
Embodiment 1:
The present embodiment is related to a kind of pair of sulfa antibiotics and the selective hollow combination die of quinolone antibiotics
The preparation method of the micro- shell of plate molecularly imprinted polymer.
A kind of preparation method of the hollow combination micro- shell of template molecularly imprinted polymer (h-MIMs), comprising the following steps:
S1, it prepares polystyrene nanoparticle: preparing the polystyrene of monodispersed carboxylic acid modification by emulsion polymerization
Nanoparticle；Firstly, the sodium bicarbonate aqueous solution that concentration is 1.5mg/mL is added in three-necked bottle and is passed through nitrogen, water by 100g
After bath is heated to 60 DEG C, the ammonium persulfate of the acrylic acid of 1g, the styrene of 5g and 0.08g is sequentially added, in the machinery of 400rmp
Under stirring, 70 DEG C of polymerization reaction 20h are centrifuged 10min in 10000rpm at room temperature, remove supernatant liquor, obtain polystyrene and receive
Rice corpuscles；After ethanol washing polystyrene nanoparticle 3 times, it is spare that drying to constant weight at 60 DEG C；
S2, prepare pre-assembled solution: it is molten for template with sulphadiazine and Ciprofloxacin, weigh 0.5mmol sulphadiazine,
0.5mmol Ciprofloxacin and 5mmol methacrylic acid are in beaker, with dimethyl sulfoxide by the concentration of sulphadiazine and Ciprofloxacin
25 μm of ol/g are diluted to, ultrasound 25min, obtains pre-assembled solution at 600W；
S3, prepare molecular engram nanosphere: the polystyrene nanoparticle for taking 0.4g step S1 to prepare is scattered in 100g,
In the lauryl sodium sulfate aqueous solution of 0.25mg/ml, emulsified 24 hours under the action of 250rpm stirring；20g step is added
The pre-assembled solution of S2 preparation continues emulsification for 24 hours under 250pm stirring；Then, 6g divinylbenzene and 0.08g azo is added
Two isobutyl cyanogen, initiated polymerization；In order to improve the shape characteristic for preparing material, polymerization reaction reacts 8h at 43 DEG C first,
20h is reacted at 60 DEG C later, finally reacts 2h at 80 DEG C；Reaction system uses 4000rpm to be centrifuged 10min at room temperature
Afterwards, supernatant liquor is removed, it is spare after drying to constant weight at 60 DEG C after sediment cleans 3 times with ethyl alcohol；
S4, it prepares hollow polymer material: weighing molecular engram nanosphere 0.5g made from step S3,45g bis- is added
Chloromethanes shakes 22h in 20 DEG C of constant temperature with 150 times/min of amplitude, is received with removing the polystyrene in molecular engram nanosphere
Rice corpuscles obtains hollow polymer material；
S5, removing template molecule: the polymer of 1.5g step S4 preparation is weighed, using Soxhlet extractor, with 120g acetic acid
Methanol solution (volume ratio of acetic acid and methanol is 1:4) is solvent, the hollow polymer material that at 70 DEG C prepared by Soxhlet extraction
In template molecule, until liquid phase tandem mass spectrum can not detect it is husky containing template molecule sulphadiazine and cyclopropyl in Soxhlet extraction liquid
Until star；The polymer for removing template molecule is washed into neutrality with deionized water, obtains h- after drying to constant weight at 60 DEG C
MIMs。
Embodiment 2
In order to verify selective absorption performance of the h-MIMs to template molecule of preparation of the embodiment of the present invention, as follows
Molecular engram material is prepared as control.
One, the preparation of the hollow micro- shell of non-molecular engram (h-NIMs) uses following steps:
1. preparing the polystyrene nanoparticle of carboxylic acid modification: method is identical as the step S1 of the embodiment of the present invention 1；
2. preparing non-molecular engram nanosphere: the polystyrene nanoparticle for taking 0.4g step 1. to prepare is scattered in
100g, 0.25g mL-1Lauryl sodium sulfate aqueous solution in, emulsified 24 hours under the action of stirring；Then, 6g bis- is added
Vinyl benzene and 0.08g azo-bis-isobutyl cyanide, initiated polymerization；In order to improve the shape characteristic for preparing material, polymerization reaction
8h is reacted at 43 DEG C first, reacts 20h at 60 DEG C later, finally reacts 2h at 80 DEG C；Reaction system is adopted at room temperature
After being centrifuged 10min with 4000rpm, supernatant liquor is removed, after sediment cleans 3 times with ethyl alcohol, after drying to constant weight at 60 DEG C
It is spare；
3. preparing the micro- shell of hollow molecules trace nanometer: weighing step 2. molecularly imprinted polymer 0.5g obtained, 45g is added
Methylene chloride, 20 DEG C with amplitude 150 times/min isothermal vibration 22h to remove polystyrene nanoparticle；It is removed with methylene chloride
After removing extra polystyrene, polymer is washed into neutrality with deionized water, obtains h- after drying to constant weight at 60 DEG C
NIMs。
Two, the preparation of surface bimodulus version molecular engram material (s-MIPs) uses following steps:
1. preparing the polystyrene nanoparticle of carboxylic acid modification: method is identical as the step S1 of the embodiment of the present invention 1；
2. preparing pre-assembled solution: method is identical as the step S2 of the embodiment of the present invention 1；
3. preparing bimodulus version molecular engram nanosphere: method is identical as the step S3 of the embodiment of the present invention 1；
4. preparing the micro- shell of surface bimodulus version molecular engram nanometer: 3. polymer that 1.5g step is prepared is weighed, using Soxhlet
Extracting process, with 120mL acetic acid methanol solution (volume ratio of acetic acid and methanol is 1:4) for solvent, the Soxhlet extraction at 70 DEG C
The 3. template molecule in polymer material that step is prepared contains mould until liquid phase tandem mass spectrum can not detect in Soxhlet extraction liquid
Until plate molecule sulphadiazine and Ciprofloxacin；The polymer for removing template molecule is washed into neutrality with deionized water, at 60 DEG C
S-MIPs is obtained after drying to constant weight down.
Three, the preparation of the non-molecular engram material in surface (s-NIPs) uses following steps:
1. preparing the polystyrene nanoparticle of carboxylic acid modification: method is identical as the step S1 of the embodiment of the present invention 1；
2. preparing non-molecular engram nanosphere: dispersing 100g for 1. polystyrene nanoparticle that 0.4g step is prepared
In the lauryl sodium sulfate aqueous solution of concentration 0.25g/mL, emulsified for 24 hours under the action of stirring；Then, 6g divinyl is added
Base benzene and 0.08g azo-bis-isobutyl cyanide, initiated polymerization, in order to improve the shape characteristic for preparing material, polymerization reaction is first
In 43 DEG C of reaction 8h, later in 60 DEG C of reaction 20h, finally in 80 DEG C of reaction 2h；Reaction system use at room temperature 4000rpm from
After heart 10min, supernatant liquor is removed, after sediment cleans 3 times with ethyl alcohol, obtains s- after drying to constant weight at 60 DEG C
NIPs。
Four, bimodulus version molecular engram material (p-MIPs) is prepared using precipitation polymerization method
The method that precipitation polymerization method prepares p-MIPs is as follows: weigh 0.5mmol sulphadiazine, 0.5mmol Ciprofloxacin and
The concentration dilution of sulphadiazine and Ciprofloxacin is by 5mmol methacrylic acid (function monomer) in beaker, with dimethyl sulfoxide
25 μm of ol/g, ultrasound 25min, obtains pre-assembled solution at 600W.6g divinylbenzene is added, ultrasonic 30min obtains pre-polymerization
Close solution；0.4g polyvinylpyrrolidone is dissolved in 80g ethyl alcohol, is transferred in 250mL three-necked bottle, nitrogen deoxygenation is simultaneously stirred
(300rpm)；By after stirring pre-polymer solution and 0.08g azo-bis-isobutyl cyanide be added into three-necked bottle, reaction system is at 60 DEG C
Under the conditions of polymerize for 24 hours；After the completion of polymerization, after reaction system uses 4000rpm to be centrifuged 10min at room temperature, supernatant liquor is removed,
Deposit Soxhlet extraction at 70 DEG C with 20% acetic acid methanol solution (the volume ratio v:v=2:8 of acetic acid and methanol), until
Until liquid phase tandem mass spectrum can not detect template molecule sulphadiazine and Ciprofloxacin；Product is washed with water later to neutrality, 60
P-MIPs is obtained after drying to constant weight at DEG C.
Five, non-molecular engram material (p-NIPs) is prepared using precipitation polymerization method
The method that precipitation polymerization method prepares p-NIPs is as follows: the methacrylic acid of 5.0mmol is dissolved in dimethyl sulfoxide
In, after making 25 μm of ol/g of concentration of methacrylic acid, 6g divinylbenzene is added, ultrasonic 30min obtains pre-polymer solution；It will
0.4g polyvinylpyrrolidone is dissolved in 80g ethyl alcohol, is transferred in 250mL three-necked bottle, and nitrogen deoxygenation simultaneously stirs (300rpm)；
By after stirring pre-polymer solution and 0.08g azo-bis-isobutyl cyanide be added into three-necked bottle, reaction system under the conditions of 60 DEG C gather
It closes for 24 hours；After the completion of polymerization, after reaction system uses 4000rpm to be centrifuged 10min at room temperature, supernatant liquor is removed.Deposit
After cleaning 3 times with ethyl alcohol, p-MIPs is obtained after drying to constant weight at 60 DEG C.
Embodiment 3
The present embodiment is related to the hollow micro- shell of gang form molecularly imprinted polymer (h-MIMs) of the preparation of the embodiment of the present invention 1
To the selective absorption performance verification of template molecule.
H-MIMs is to the h-MIMs and h- that the selective evaluation of sulfanilamide (SN) and quinolone antibiotics is by comparison synthesis
NIMs to template molecule (sulphadiazine SDZ and Ciprofloxacin CIP), (sulfamethyldiazine SMR, sulfanilamide (SN) are to first for analogue
Oxygen pyrimidine SMD, daimeton SMM, sulfamethoxazole SMX madribon SDM, sulfanilamide (SN) quinoline dislike woods SQX, a left side
Ofloxacin LVX, Lomefloxacin LOM and Enrofloxacin ENR) and reference compound (oestrone Estrone and Erythromycin E M) suction
Attached sex differernce is completed.It is respectively 0.1mmol/L's with adsorbent (h-MIMs, h-NIMs) the absorption 2.0mL concentration of 20mg
Template molecule, analogue and reference compound.It stands at room temperature for 24 hours, then by supernatant separation filter analysis.Template point
Son, analogue and the amount of reference compound reduction are adsorbent amount, as a result as shown in Figure 1.H-MIMs is to two
Kind template and its analogue have preferable selectivity, but poor for the selectivity of Estrone and EM, especially for
EM, mainly since its molecular weight is larger, occupied space is greater than what imprinted cavity can provide.
Embodiment 4
This embodiment is related to the micro- shell (h- of hollow gang form molecularly imprinted polymer of the preparation of the embodiment of the present invention 1
MIMs the verifying of Static Adsorptive capacity).
H-MIMs is by comparison distinct methods preparation to the Static Adsorptive capacity evaluation of sulfanilamide (SN) and quinolone template molecule
Molecular engram material, including h-MIMs, h-NIMs, p-MIPs, p-NIPs, s-MIPs and s-NIPs are to sulphadiazine and cyclopropyl
The adsorbance difference of Sha Xing is completed.Adsorbent (h-MIMs, h-NIMs, p-MIPs, p-NIPs, s- of 20mg are used respectively
MIPs and s-NIPs) sulphadiazine and ciprofloxacin solution that 2.0mL concentration is 0.5mmol/L are adsorbed, after standing for 24 hours at room temperature
It is analyzed after supernatant separation is filtered, the results are shown in Table 1.Adsorbance of six kinds of polymer for sulfanilamide (SN) and Ciprofloxacin
Sequence from high to low is respectively h-MIMs > p-MIPs > s-MIPs > h-NIMs > p-NIPs > s-NIPs.It is found that the suction of h-MIMs
Attached amount highest, while the adsorbance of MIPs is apparently higher than the adsorbance of NIPs.
Adsorbance (mmol/g) of the different adsorbents of table 1 to template molecule sulphadiazine and Ciprofloxacin
Embodiment 5
This embodiment is related to the micro- shell (h- of hollow gang form molecularly imprinted polymer of the preparation of the embodiment of the present invention 1
MIMs the verifying of dynamic adsorption).
H-MIMs is by comparison distinct methods preparation to the dynamic adsorption evaluation of sulfanilamide (SN) and quinolone template molecule
Molecular engram material, including h-MIMs, p-MIPs and s-MIPs to the adsorbance rate difference of sulphadiazine and Ciprofloxacin
Come what is completed.It is respectively 0.1mmol/L's with adsorbent (h-MIMs, p-MIPs and s-MIPs) the absorption 2.0mL concentration of 20mg
Sulphadiazine and ciprofloxacin solution.Mixture is stood at 25 DEG C, monitors sulphadiazine and Ciprofloxacin in solution using HPLC,
Thus the dynamic adsorption of three kinds of materials is studied, as a result as shown in Figure 2.Absorption of six kinds of polymer for sulfanilamide (SN) and quinolone
The sequence of rate from high to low is respectively h-MIMs > s-MIP > p-MIPs.It is found that the rate of adsorption of h-MIMs is most fast.
Embodiment 6
This embodiment is related to the micro- shell (h- of hollow gang form molecularly imprinted polymer of the preparation of the embodiment of the present invention 1
MIMs) to the analysis of sulfanilamide (SN) and quinolone antibiotics in the different flesh of fish.
H-MIMs is to the h-MIMs material conduct that the analysis of sulfanilamide (SN) in the flesh of fish and quinolone antibiotics is by that will prepare
Solid phase extraction adsorbents are applied in the stochastic buying flesh of fish sample of market in the analysis of sulfanilamide (SN) and quinolone, and more our
The difference of method and other matrix effects of non-selective solid phase extraction adsorbents in the assay evaluates its selective absorption effect.
One, analysis of the h-MIMs as solid phase extraction adsorbents to sulfanilamide (SN) and quinolone antibiotics in different flesh of fish samples
Solid-phase extraction column used in experiment is that the 100mg embodiment of the present invention 1 is added in empty polytetrafluoroethylene (PTFE) pillar
Made of the h-MIMs of preparation.This extraction column uses 3.0mL methanol and 3.0mL distilled water to activate spare respectively later.1.0g fish
After meat sample product and 10.0mL acetonitrile stir 10min in 25mL beaker, it is transferred in 50.0mL centrifuge tube.At 4500rpm from
After heart 5min, after upper solution is evaporated with Rotary Evaporators, with 1.0mL acetonitrile back dissolving, later with after the dilution of 6.0mL water, with
0.8mL/min is eluted with the methanol aqueous solution of 2.0mL 20%, by the extraction column after above-mentioned activation finally, using 1.5mL later
Acetic acid acetonitrile solution (5/95, v/v) elution.Enter HPLC-MS/MS after 0.45 μm of membrane filtration of eluent to measure.
Two, the analysis using conventional method to sulfanilamide (SN) in the flesh of fish and quinolone antibiotics
Solid-phase extraction column used in experiment is commercialized Oasis HLB (100mg, 3mL) solid phase extraction column.Later
It is spare that this extraction column uses 3.0mL methanol and 3.0mL distilled water to activate respectively.1.0g flesh of fish sample and 10.0mL acetonitrile are in 25mL
After stirring 10min in beaker, it is transferred in 50.0mL centrifuge tube.After being centrifuged 10min at 4500rpm, upper solution is revolved
Turn after evaporimeter is evaporated, with 1.0mL acetonitrile back dissolving, later with after the dilution of 6.0mL water, with 0.8mL/min by above-mentioned activation after
Extraction column, later with 2.0mL aqueous solution elute, finally, with 1.0mL acetonitrile elute.0.45 μm of membrane filtration of eluent
Enter HPLC-MS/MS afterwards to measure.
Above two method applies result such as table 2 in the flesh of fish, and h-MIMs of the invention is used to adsorb as Solid Phase Extraction
11 kinds of sulfanilamide (SN) or quinolone antibiotics are not detected in agent in opium fish and Spanish mackerel, and detect in carp and crucian a small amount of
SMD detects a small amount of SMD (3.2 ± 0.1ng g in silver carp-1) and LVX, obtained result and traditional analysis method knot
Fruit is consistent, it was demonstrated that the accuracy that is detected using h-MIMs of the present invention.
2 present invention of table is applied to the analysis of sulfanilamide (SN) and quinolone antibiotics in flesh of fish sample
(unit is ng g-1, mean+SD, n=3)
Remarks: LOQ is content limit, and "-" expression is not detected.
The results are shown in Table 3 for the matrix effect of two methods, and numerical value is greater than zero and represents matrix enhancement effect, and numerical value is less than zero
Indicate substrate inhibition effect.
Table 3h-MIMs is solid extracting agent and conventional method matrix effect comparison sheet
Using h-MIMs as the substrate inhibition effect of the sample-pretreating method of solid phase extraction adsorbents be 7.4%~
13.5%, and the matrix effect of traditional solid phase extraction adsorbents is 22.8%~41.4%.The result shows that being solid with h-MIMs
Mutually the sample-pretreating method of extraction adsorbent is compared to traditional C18Adsorbent greatly reduces the matrix effect of method.?
In mass spectral analysis, coextraction object is to generate matrix effect principal element.And molecular engram material is due to selective absorption performance
It is good, the type and number of coextraction substance are greatly reduced, the reduction of matrix effect is caused.
Embodiment 7
The present embodiment is related to a kind of pair of sulfa antibiotics and the selective hollow combination die of quinolone antibiotics
The preparation method of the micro- shell of plate molecularly imprinted polymer.
A kind of preparation method of the hollow micro- shell of gang form molecularly imprinted polymer, comprising the following steps:
S1, it prepares polystyrene nanoparticle: preparing the polystyrene of monodispersed carboxylic acid modification by emulsion polymerization
Nanoparticle；Firstly, the sodium bicarbonate aqueous solution that concentration is 2.0mg/mL is added in three-necked bottle and is passed through nitrogen, water-bath by 80g
After being heated to 55 DEG C, the ammonium persulfate of the acrylic acid of 0.5g, the styrene of 6.0g and 0.05g is sequentially added, in the machine of 350rmp
Under tool stirring, polymerization reaction 15h at a temperature of 68 DEG C removes supernatant liquor using 8000rpm centrifugation 5min at room temperature, obtains
To polystyrene nanoparticle；It is spare after drying to constant weight at 40 DEG C using ethanol washing polystyrene nanoparticle 5 times；
S2, it prepares pre-assembled solution: weighing sulphadiazine 0.3mmol, Ciprofloxacin 0.3mmol and methacrylic acid
2.4mmol is diluted to 50 μm of ol/g in beaker, with dimethyl sulfoxide, and the ultrasound 20min under 500W power is obtained pre-assembled molten
Liquid；
S3, molecular engram nanosphere is prepared: the polystyrene nanoparticle for taking 0.3g step S1 to prepare, in ultrasonication
Under be dispersed in 80g, in the lauryl sodium sulfate aqueous solution of 0.3g/mL, stirred emulsified 20 hours in 350rpm；It is added
The pre-assembled solution of 10g step S2 preparation continues to emulsify 20h under 350rpm stirring；Then, the crosslinking agent divinyl of 3g is added
The initiator azo-bis-isobutyl cyanide of base benzene and 0.05g, initiated polymerization；In order to improve the shape characteristic for preparing material, it polymerize
The temperature that reaction occurs is temperature programming, condition are as follows: 40 DEG C are reacted 6 hours, and 55 DEG C are reacted 18 hours, and 75 DEG C are reacted 1 hour；Instead
After answering system that 3500rpm is used to be centrifuged 10min at room temperature, supernatant liquor is removed, sediment cleans 3 times with ethyl alcohol and removes wherein
Impurity, it is spare after drying to constant weight at 50 DEG C；
S4, it prepares hollow polymer material: weighing molecular engram nanosphere 0.4g made from step S3,30g bis- is added
Chloromethanes, 18 DEG C of constant temperature, 160 times/min shake the polystyrene nanoparticle in 20h removing molecular engram nanosphere, obtain
Hollow polymer material；
S5, removing template molecule: the polymer for weighing 2g step S4 preparation uses 150g acetic acid using Soxhlet extractor
Methanol (1:3, v/v) is solvent, the template molecule in hollow polymer material that at 68 DEG C prepared by extraction step S4, to remove
Template molecule；With deionized water the polymer for removing template molecule is washed into neutrality, is obtained after drying to constant weight at 55 DEG C
The micro- shell of idle pattern template molecule imprinted polymer.
Embodiment 8
A kind of preparation method of the hollow micro- shell of gang form molecularly imprinted polymer, comprising the following steps:
S1, it prepares polystyrene nanoparticle: preparing the polystyrene of monodispersed carboxylic acid modification by emulsion polymerization
Nanoparticle；Firstly, the sodium bicarbonate aqueous solution that concentration is 1mg/mL is added in three-necked bottle and is passed through nitrogen, water-bath by 120g
After being heated to 65 DEG C, the ammonium persulfate of the acrylic acid of 1.5g, the styrene of 4.0g and 0.1g is sequentially added, in the machinery of 450rmp
Under stirring, polymerization reaction 25h at a temperature of 72 DEG C removes supernatant liquor using 9000rpm centrifugation 8min at room temperature, obtains
Polystyrene nanoparticle；It is spare after drying to constant weight at 50 DEG C using ethanol washing polystyrene nanoparticle 4 times；
S2, it prepares pre-assembled solution: weighing sulphadiazine 0.6mmol, Ciprofloxacin 0.6mmol and methacrylic acid
7.2mmol is added dimethyl sulfoxide for sulphadiazine and is diluted to 38 μm of ol/g, ultrasound 22min, obtains under 800W power in beaker
To pre-assembled solution；
S3, molecular engram nanosphere is prepared: the polystyrene nanoparticle for taking 0.5g step S1 to prepare, in ultrasonication
Under be dispersed in 150g, in the lauryl sodium sulfate aqueous solution of 0.2g/mL, stirred emulsified 28 hours in 300rpm；Add
The pre-assembled solution for entering 25g step S2 preparation continues to emulsify 28h under 300rpm stirring；Then, the crosslinking agent diethyl of 9g is added
The initiator azo-bis-isobutyl cyanide of alkenyl benzene and 0.1g, initiated polymerization；In order to improve the shape characteristic for preparing material, it polymerize
The temperature that reaction occurs is temperature programming, condition are as follows: 45 DEG C are reacted 10 hours, and 65 DEG C are reacted 25 hours, and 78 DEG C are reacted 3 hours；
After reaction system uses 4500rpm to be centrifuged 10min at room temperature, supernatant liquor is removed, sediment cleans 4 times with ethyl alcohol and removes it
Middle impurity, it is spare after drying to constant weight at 55 DEG C；
S4, it prepares hollow polymer material: weighing molecular engram nanosphere 0.6g made from step S3,50g bis- is added
Chloromethanes, 22 DEG C of constant temperature, 140 times/min concussion remove the polystyrene nanoparticle in molecular engram nanosphere for 24 hours, obtain
Hollow polymer material；
S5, removing template molecule: the polymer for weighing 1g step S4 preparation uses 100g acetic acid using Soxhlet extractor
Methanol (1:5, v/v) is solvent, the template molecule in hollow polymer material that at 72 DEG C prepared by extraction step S4, to remove
Template molecule；With deionized water the polymer for removing template molecule is washed into neutrality, is obtained after drying to constant weight at 60 DEG C
The micro- shell of idle pattern template molecule imprinted polymer.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art within the technical scope of the present disclosure, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (13)
1. a kind of preparation method of the hollow micro- shell of gang form molecularly imprinted polymer, which comprises the steps of:
S1, it prepares polystyrene nanoparticle: styrene, acrylic acid being dispersed in sodium bicarbonate aqueous solution, in nitrogen protection
Under, initiator ammonium sulfate is added by polymerization reaction and obtains polystyrene nanoparticle；
S2, pre-assembled solution is prepared: using sulphadiazine and Ciprofloxacin as template, using methacrylic acid as function monomer, by mould
Plate and function monomer, which are scattered in dimethyl sulfoxide, to be dissolved, and pre-assembled solution is obtained；
S3, it prepares molecular engram nanosphere: the step S1 polystyrene nanoparticle prepared is dispersed in dodecanoic acid
In aqueous sodium persulfate solution, pre-assembled solution, cross-linker divinylbenzene and the initiator azo two of step S2 preparation are sequentially added
Isobutyl cyanogen obtains molecular engram nanosphere by polymerization reaction；
S4, prepare hollow polymer material: molecular engram nanosphere prepared by step S3 removes polystyrene, obtains hollow poly-
Close object material；
S5, removing template molecule: soxhlet extraction method is used, the hollow polymeric prepared using acetic acid methanol solution removal step S4
Template molecule sulphadiazine and Ciprofloxacin in object material obtain the hollow micro- shell of gang form molecularly imprinted polymer.
2. the preparation method of the hollow micro- shell of gang form molecularly imprinted polymer according to claim 1, which is characterized in that step
Polystyrene nanoparticle described in rapid S1 the preparation method comprises the following steps: logical in the sodium bicarbonate aqueous solution that concentration is 1.0~2.0mg/mL
Enter nitrogen, heating water bath sequentially adds acrylic acid, styrene and ammonium persulfate, in the machine of 350~450rmp to after 55~65 DEG C
Under tool stirring, 15~25h of polymerization reaction at a temperature of 68~72 DEG C；At room temperature using 8000~10000rpm centrifugation 5~
10min removes supernatant liquor, obtains polystyrene nanoparticle；Using ethanol washing polystyrene nanoparticle 3~5 times,
It is spare after drying to constant weight at 40~60 DEG C.
3. the preparation method of the hollow micro- shell of gang form molecularly imprinted polymer, feature exist according to claim 2
In the weight ratio of 1.0~2.0mg/mL sodium bicarbonate solution, acrylic acid, styrene, ammonium persulfate additive amount are as follows: (80~
120): (0.5~1.5): (4.0~6.0): (0.05~0.1).
4. the preparation method of the hollow micro- shell of gang form molecularly imprinted polymer according to claim 1, which is characterized in that step
Prepare described in rapid S2 pre-assembled solution the preparation method comprises the following steps: being 1:1:(8~12 by molar ratio) sulphadiazine, Ciprofloxacin and
Methacrylic acid is added in beaker, is 25~50 μm of ol/g, 500~800W function with the concentration that dimethyl sulfoxide is diluted to sulphadiazine
20~25min of ultrasound, obtains pre-assembled solution under rate.
5. the preparation method of the hollow micro- shell of gang form molecularly imprinted polymer according to claim 1, which is characterized in that step
The method of molecular engram nanosphere is prepared described in rapid S3 are as follows: the polystyrene nanoparticle for preparing step S1, it is evenly dispersed
In the lauryl sodium sulfate aqueous solution of 0.2~0.3mg/mL, emulsified 20~28 hours in the stirring of 250~350rpm；
The pre-assembled solution that step S2 preparation is added continues 20~28h of emulsification under the stirring of 250~350rpm；Then, it is added and hands over
Join agent divinylbenzene and initiator azo-bis-isobutyl cyanide, initiated polymerization: 40~45 DEG C are reacted 6~10 hours, and 55~65
DEG C reaction 18~25 hours, 75~80 DEG C react 1~3 hour；Reaction system uses 3500~4500rpm to be centrifuged at room temperature
10min removes supernatant liquor, and sediment cleans 3~4 removing impurity with ethyl alcohol, and drying to constant weight at 50~60 DEG C, score
Sub- trace nanosphere.
6. the preparation method of the hollow micro- shell of gang form molecularly imprinted polymer according to claim 5, which is characterized in that institute
State polystyrene nanoparticle, 0.2~0.3g/mL lauryl sodium sulfate aqueous solution, pre-assembled solution, divinylbenzene, idol
The weight ratio of two isobutyl cyanogen additive amount of nitrogen is (0.3~0.5): (80~150): (10~25): (3~9): (0.05~0.10).
7. the preparation method of the hollow micro- shell of gang form molecularly imprinted polymer according to claim 1, which is characterized in that step
The method of hollow polymer material is prepared described in rapid S4 are as follows: dichloromethane is added in the molecular engram nanosphere for preparing step S3
Alkane, 18~22 DEG C of constant temperature, 140~160 times/min concussion 20~for 24 hours remove molecular engram nanosphere in pipe/polyhenylethylene nano
Particle, gained are precipitated as hollow polymer material.
8. the preparation method of the hollow micro- shell of gang form molecularly imprinted polymer according to claim 7, which is characterized in that institute
The weight ratio for stating molecular engram nanosphere and methylene chloride additive amount is (0.4~0.6): (30~50).
9. the preparation method of the hollow micro- shell of gang form molecularly imprinted polymer according to claim 1, which is characterized in that step
The method of template molecule is removed described in rapid S5 are as follows: soxhlet extraction is utilized, it is molten using the acetic acid methanol that volume ratio is 1:3~1:5
Liquid is solvent, the template molecule in hollow polymer material that at 68~72 DEG C prepared by extraction step S4；It will with deionized water
The polymer for removing template molecule washes neutrality, and hollow gang form molecular engram is obtained after drying to constant weight at 55~60 DEG C
The micro- shell of polymer.
10. the preparation method of the hollow micro- shell of gang form molecularly imprinted polymer according to claim 9, which is characterized in that
In the Soxhlet extraction, the weight ratio of acetic acid methanol solution and hollow polymer usage amount that volume ratio is 1:3~1:5 is (100
~150): (1~2).
11. a kind of application of the hollow micro- shell of gang form molecularly imprinted polymer of claims 1 to 10 either method preparation,
It is characterized in that, sulfa antibiotics and/or quinolone antibiotics is enriched with.
12. the application of the hollow micro- shell of gang form molecularly imprinted polymer according to claim 11, which is characterized in that described
Sulfa antibiotics include sulphadiazine, sulfamethyldiazine, 5-methoxysulfadiazine, daimeton, sulfalene evil
Azoles, madribon, sulfanilamide (SN) quinoline dislike one of woods or a variety of.
13. the application of the hollow micro- shell of gang form molecularly imprinted polymer according to claim 12, which is characterized in that described
Quinolone antibiotics include: one of Ciprofloxacin, lavo-ofloxacin, Lomefloxacin, Enrofloxacin or a variety of.
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