CN105175611A - Preparation method of molecularly imprinted polymer packing for fluoroquinolone antibiotics - Google Patents
Preparation method of molecularly imprinted polymer packing for fluoroquinolone antibiotics Download PDFInfo
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- CN105175611A CN105175611A CN201510631703.9A CN201510631703A CN105175611A CN 105175611 A CN105175611 A CN 105175611A CN 201510631703 A CN201510631703 A CN 201510631703A CN 105175611 A CN105175611 A CN 105175611A
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Abstract
The invention provides a preparation method of molecularly imprinted polymer packing for fluoroquinolone antibiotics. The method includes the steps that tetraethoxysilane serves as a silicon source, polyether F127 serves as a template, and nanometer meso-porous silicon particles are prepared in a CTAB-water system; the nanometer meso-porous silicon particles are subjected to amino-group functionalization, and glucose serves as a carbon source to prepare unloaded nanometer mesoporous carbon particles; methacrylic acid serves as monomers, trimethoxy propyl acrylate serves as a crosslinking agent, MCNs and norfloxacin to which functional groups are added serve as template molecules, and nanometer mesoporous carbon loaded with molecularly imprinted polymer is prepared. The molecularly imprinted polymer packing has the recognition and selective adsorption functions on the fluoroquinolone antibiotics, the adsorption effect is remarkably improved, and recovery and regeneration are easy.
Description
Technical field
What the present invention relates to is the technology of a kind of environment and Material Field, specifically a kind of preparation method of the molecularly imprinted polymer filler for fluoroquinolone antibiotics.
Background technology
At present, can be used for the filler that in water, microbiotic is removed and comprise gac, bio-modification sludge carbon, polymeric adsorbent etc.The general character of these fillers is: do not select specificity to the absorption of water pollutant, and adsorption process exists competitive adsorption, and this is not easy to the removal of underwater trace pollutent.This is because when adopting these adsorption stuffings, contaminant trace species always can be disturbed by other materials in water, makes filler decline to the adsorption efficiency of these contaminant trace species.For example, fluoroquinolone antibiotics is large mainly with Gamma Magnitude in water surrounding, even nanogram level exists, even and if the existence of antibiotics medicine trace also can cause potential danger to the ecosystem, there is/bring out various microbial state treatment or infection, as microbiotic diarrhoea, septicemia, pseudomembranous enterocolitis etc.But fluoroquinolone antibiotics can not be removed completely in water, its effective removal pathway is absorption and chemical oxidation.If can adopt to have selects narrow spectrum filler to remove fluoroquinolones material in water targetedly, retain the existence of other mineral substance in tap water simultaneously, not only reduce the risk that microbiotic brings in tap water, the existence to human body beneficiating ingredient in tap water can also be ensured.
The work such as molecular imprinting can identify target molecule effectively, detect, analyze, separation.The polymer phase of preparation, for crude substance, has same recognition capability, has more the stability of high temperature resistance high pressure, anti-strong acid alkali salt, anti-adverse environment, and reusable.The feature of the precordainment of molecular imprinting, higher identity and practicality, is conducive to effective removal of specific pollutants.
Through finding the retrieval of prior art, Chinese patent literature CN104828802A, day for announcing 2015.8.12, disclose a kind of synthetic method and application of meso-porous carbon material of efficient adsorption tsiklomitsin, using tensio-active agent blocked polyethers F ?127 as template, resol is as carbon source, and tetraethoxy is the synthesising mesoporous carbon material in silicon source; Preparation process is as follows: first using segmented copolymer F ?127 amphipathic molecules as mould material, with tetraethoxy be silicon source, resol for carbon source presoma blended, recycling solvent evaporates self-assembly method, obtaining complex carbon material through volatilization, solidification, high-temperature roasting, finally obtain meso-porous carbon material in drying after hydrofluoric acid wash.But this technology does not possess the function that adsorption selection removes fluoroquinolone antibiotics, and this material does not possess recognition function to target contaminant, and material require could regenerate through high temperature.
Summary of the invention
The present invention is directed to prior art above shortcomings, a kind of preparation method of the molecularly imprinted polymer filler for fluoroquinolone antibiotics is proposed, with mesoporous nano carbon for carrier, to fluoroquinolone antibiotics, there is identification and selective adsorption function, and its regeneration only needs with organic solvent wash-out, clearance is high, is easy to regeneration, reusable.
The present invention is achieved by the following technical solutions:
The present invention take methacrylic acid as monomer, and trimethoxy oxypropyl trimethyl acrylate is linking agent, with the mesoporous nano carbon of functionalization and norfloxicin for template molecule, prepares molecularly imprinted polymer filler by polyreaction.
The present invention specifically comprises the steps:
Step 1, be silicon source with tetraethoxy, triblock copolymer is template, prepares mesoporous nano silicon particle (MesoporousSilicaNanoparticles, MSNs) in CTAB-water system.
Step 2, by carrying out aminofunctional to MSNs, be that carbon source prepares unloaded mesoporous nano carbon particulate (MesoporousCarbonNanoparticles, MCNs) with glucose.
Step 3, with methacrylic acid (Methacrylicacid, MAA) be monomer, trimethoxy oxypropyl trimethyl acrylate (TRIM) is linking agent, with the MCNs of functionalization and norfloxicin for template molecule, the mesoporous nano carbon (Molecularlyimprintedpolymer ?MCNs, MIP ?MCNs) of molecularly imprinted polymer is carried in preparation.
Technique effect
Compared with prior art, the present invention has the function of identification and adsorption selection to fluoroquinolone antibiotics, and adsorption effect is significantly increased; When regenerating, only need to adopt organic solvent to carry out wash-out to molecularly imprinted polymer, vacate a position, organic efficiency is high; In preparation process, introduce olefin group at mesoporous nano carbon surface, make molecularly imprinted polymer can be combined in mesoporous nano carbon surface securely, there is good chemical stability.
Accompanying drawing explanation
Fig. 1 is schematic diagram of the present invention;
Fig. 2 is schema of the present invention;
Fig. 3 is embodiment 2 experimental result picture.
Embodiment
Elaborate to embodiments of the invention below, the present embodiment is implemented under premised on technical solution of the present invention, give detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
As depicted in figs. 1 and 2, the present embodiment if no special instructions, all carries out, comprises the following steps at room temperature 25 DEG C:
Step 1, preparation, without molecular imprinting mesoporous nano carbon particulate (MesoporousCarbonNanoparticles, MCNs), specifically comprise:
Step 1.1) prepare mesoporous nano silicon particle (MesoporousSilicaNanoparticles, MSNs), comprise the following steps:
1.1.1) solution A is prepared: successively by 0.5g cetyl trimethylammonium bromide (Cetyltrimethylammoniumbormide, CTAB), 2.05g triblock copolymer polyethers F127 joins in 96mL distilled water and mixes, again by the strong aqua (2.5wt%) of 11.25mL (10.05g) the slowly above-mentioned mixed solution of instillation, mixing.
1.1.2) solution B is prepared: joined in the dehydrated alcohol of 43.04mL (34g) by the tetraethoxy (Tetraethylorthosilicate, TEOS) of 1.93mL (1.8g).
1.1.3) solution B is poured into rapidly in solution A, 80 DEG C, 1000rpm magnetic agitation 1min, left at room temperature 24h.
1.1.4) by the mixing solutions centrifugal 20min under 13000rpm after leaving standstill, remove supernatant, by white precipitate washed with de-ionized water 2 times, be placed in 70 DEG C of dry 10h of baking oven, form 2.5g white crystals body.
1.1.5) sample after centrifugal is placed in stainless steel cauldron, at 130 ~ 150 DEG C, react 2d.
1.1.6) by sample at 550 DEG C, calcine 6h crystallization under normal pressure, namely obtain the black crystals of MSNs.
Step 1.2) MSNs aminofunctional, specifically comprise:
1.2.1) the MSNs crystal obtained is put into the toluene of 98.8mL and 1.2mL 3 ?aminopropyl triethoxysilane (3 ?aminopropyltriethoxysilane, APTES) mixing solutions, at 180 DEG C, while pass into N
2limit reaction 12h.
1.2.2) reacted sample is centrifugal under 12000prm, washing with alcohol throw out, by the 2.0g solid of gained at 110 DEG C of vacuum drying 10h.
Step 1.3) prepare MCNs, specifically comprise:
1.3.1) 0.5g step 1.2 is taken) solid that obtains joins in the glucose solution of 40mL (1.25M), and ultrasonic vibration, makes it to be uniformly dispersed.
1.3.2) solution previous step obtained 180 DEG C of water-bath 3h.
1.3.3) solution previous step obtained is centrifugal 20min under 13000rpm, and the brown precipitate thing obtained uses water and washing with alcohol 3 times respectively, dry at 100 DEG C.
1.3.4) brown solid previous step obtained carries out carbonization at 900 DEG C, namely obtains 0.6gMCNs.
Step 2, molecularly imprinted polymer mesoporous nano carbon particulate (MIP ?MCNs) for the preparation of fluoroquinolone antibiotics, specifically comprise:
Step 2.1) MCNs is Carboxylation:
MCNs solid 1g step 1 obtained is added to the HNO of 250mL
3in solution, ultrasonic 30min, stirs 12h at 65 DEG C, and now MCNs has carboxyl to generate on the surface, namely MCNs ?COOH.
Step 2.2) prepare MSNs ?COCl, specifically comprise:
2.2.1) in order to by MCNs ?COOH separate, by above-mentioned solution centrifugal 5min under 13000rpm rotating speed, vacuum-drying.
2.2.2) take 0.4gMCNs ?COOH solid, be added to containing 10mLSOCl
2and 30mLCCl
3mixed solution in, reflux at 60 DEG C 24h.
2.2.3) with anhydrous tetrahydro furan (etrahydrofuran, THF) drip washing, to remove superfluous SOCl
2, vacuum-drying, namely generate MSNs ?COCl.
Step 2.3) prepare MCN ?CH=CH
2, specifically comprise:
2.3.1) by the MSNs of 0.2g ?COCl join 30mL containing anhydrous THF, 1.16g vinyl carbinol, 0.244g dimethylamine and 6.06g triethylamine mixed solution in.
2.3.2) mixture previous step obtained stirs 24h at 50 DEG C, then centrifugal under 13000rpm, with anhydrous THF drip washing, vacuum-drying, namely obtain MCN ?CH=CH
2.
Step 2.4) for the preparation of fluoroquinolone antibiotics MIP ?MCNs, specifically comprise:
2.4.1) in 100mL round-bottomed flask, add 50mL dry toluene, get 60mg step 2.3) obtained MCN ?CH=C
h2be added in round-bottomed flask, ultrasonic reaction 30min.
2.4.2) norfloxicin of 0.6mmol and the MAA of 3mmol are joined in round-bottomed flask, stir 30min, then add 3mmol TRIM and 30mg Ou Dan ?isopropyl cyanide (Azo ?isobutyronitrile, AIBN).
2.4.3) with the above-mentioned mixed solution 10min of N2 stripping, at 70 DEG C, 24h is stirred; Then centrifugal 5min under 13000rpm, leaves solid matter 80mg.
2.4.4) with MeOH/ acetic acid (volume ratio 9:1) the above-mentioned solid matter of drip washing under ultrasound condition, until can't detect the norfloxicin in solution with high performance liquid chromatography.
2.4.5) obtained filtrate is used ethanol rinse further, to remove residual acetic acid, then dry under vacuum drier.Now namely obtain for fluoroquinolone antibiotics MIP ?MCNs.
Embodiment 2
As shown in Figure 3, respectively by the MIP of 2mg ?the MCNs (filler B) of MCNs (filler A) and 2mg be added to that 3mL concentration is respectively 0, in the norfloxicin solution of 0.5mg/L, 5mg/L, 10mg/L, 15mg/L, 20mg/L, 40mg/L, 60mg/L, 80mg/L, 100mg/L, 120mg/L and 160mg/L, 25 DEG C, the flask that mixed solution is housed is put into constant temperature oscillator reaction 24h under the condition of 250rpm; Then the solid in mixed solution is taken out, centrifugal 5min under 13000rpm, gets 0.5mL supernatant liquor and carries out efficient liquid phase chromatographic analysis, and detect the norfloxicin content be adsorbed on solid, result as shown in Figure 3.
Result shows: the adsorption effect of filler A is obviously better than filler B.And raise along with the concentration of norfloxicin in water, the adsorption rate of two fillers declines all to some extent, but filler A then enhances relative to the removal ability of filler B; According to adsorption isotherm thread test, every gram of adsorbable norfloxicin 40.98mg of filler A, every gram of adsorbable norfloxicin 15.58g of filler B.
Claims (7)
1. the preparation method for the molecularly imprinted polymer filler of fluoroquinolone antibiotics, it is characterized in that, take methacrylic acid as monomer, trimethoxy oxypropyl trimethyl acrylate is linking agent, with the mesoporous nano carbon of functionalization and norfloxicin for template molecule, prepare molecularly imprinted polymer filler by polyreaction.
2. preparation method according to claim 1, is characterized in that, specifically comprises the steps:
Step 1, be silicon source with tetraethoxy, triblock copolymer polyethers F127 is template, prepares mesoporous nano silicon particle in CTAB-water system;
Step 2, by carrying out aminofunctional to MSNs, take glucose as the unloaded mesoporous nano carbon particulate of carbon source preparation;
Step 3, be monomer with methacrylic acid, trimethoxy oxypropyl trimethyl acrylate is linking agent, and to add the MCNs of functional group and norfloxicin for template molecule, the mesoporous nano carbon of molecularly imprinted polymer is carried in preparation.
3. preparation method according to claim 2, it is characterized in that, described step 1 comprises: react with the tetraethoxy being dissolved in dehydrated alcohol by the water mixed liquid of cetyl trimethylammonium bromide and polyethers F127, obtains mesoporous nano silicon particle successively after magnetic agitation, left at room temperature, centrifugal, oven dry and calcination crystallization.
4. preparation method according to claim 2, is characterized in that, the described MSNs that carries out carries out aminofunctional and refers to: toluene and 3 ?the mixing solutions of aminopropyl triethoxysilane, passing into N
2condition under react with MSNs.
5. preparation method according to claim 4, is characterized in that, described toluene and the volume ratio of APTES are 98.8:1.2.
6. preparation method according to claim 4, is characterized in that, described temperature of reaction is 180.
7. preparation method according to claim 1, is characterized in that, described step 3 comprises: pass through HNO
3solution is Carboxylation to MCNs, pass through SOCl
2and CCl
3mixed solution acetyl chloro substitute carboxyl, prepare MCN ?CH=CH by tetrahydrofuran (THF), vinyl carbinol, dimethylamine and triethylamine
2.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107141406A (en) * | 2017-05-26 | 2017-09-08 | 浙江海洋大学 | A kind of Magnetic Carboxylate nano-crystal cellulose amino functional molecular imprinted polymer on surface |
| CN111268814A (en) * | 2020-01-07 | 2020-06-12 | 昆明理工大学 | Anthracycline wastewater treatment method combining porous carbon nanosphere-based surface molecularly imprinted filter material and ultrafiltration molecularly imprinted membrane |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101907571A (en) * | 2010-06-28 | 2010-12-08 | 济南大学 | Mesoporous carbon molecular imprinting detector for detecting trace environment hormones and application thereof |
| CN104828802A (en) * | 2015-01-19 | 2015-08-12 | 江苏大学 | Synthetic method and application of mesoporous carbon material high-effectively adsorbing tetracycline |
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2015
- 2015-09-29 CN CN201510631703.9A patent/CN105175611A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101907571A (en) * | 2010-06-28 | 2010-12-08 | 济南大学 | Mesoporous carbon molecular imprinting detector for detecting trace environment hormones and application thereof |
| CN104828802A (en) * | 2015-01-19 | 2015-08-12 | 江苏大学 | Synthetic method and application of mesoporous carbon material high-effectively adsorbing tetracycline |
Non-Patent Citations (1)
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| 孙大明: ""分子印迹纳米粒子的制备、表征及其对氟喹诺酮的吸附特性"", 《中国优秀硕士学位论文全文数据库（电子期刊）》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107141406A (en) * | 2017-05-26 | 2017-09-08 | 浙江海洋大学 | A kind of Magnetic Carboxylate nano-crystal cellulose amino functional molecular imprinted polymer on surface |
| CN107141406B (en) * | 2017-05-26 | 2019-05-14 | 浙江海洋大学 | A kind of Magnetic Carboxylate nano-crystal cellulose amino functional molecular imprinted polymer on surface |
| CN111268814A (en) * | 2020-01-07 | 2020-06-12 | 昆明理工大学 | Anthracycline wastewater treatment method combining porous carbon nanosphere-based surface molecularly imprinted filter material and ultrafiltration molecularly imprinted membrane |
| CN111268814B (en) * | 2020-01-07 | 2022-05-24 | 昆明理工大学 | Anthracycline wastewater treatment method combining porous carbon nanosphere-based surface molecularly imprinted filter material and ultrafiltration molecularly imprinted membrane |
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Application publication date: 20151223 |