CN105170112A - Preparation method for magnetic carbon microsphere surface cephalexin molecular imprinted adsorbent material - Google Patents
Preparation method for magnetic carbon microsphere surface cephalexin molecular imprinted adsorbent material Download PDFInfo
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- CN105170112A CN105170112A CN201510444031.0A CN201510444031A CN105170112A CN 105170112 A CN105170112 A CN 105170112A CN 201510444031 A CN201510444031 A CN 201510444031A CN 105170112 A CN105170112 A CN 105170112A
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Abstract
The present invention relates to a preparation method for a magnetic carbon microsphere surface cephalexin molecular imprinted adsorbent material. The method comprises: taking a walnut shell as a carbon source to prepare a magnetic carbon microsphere; carrying out ethylene functionalized modification on the surface of the magnetic carbon microsphere by use of 3-(methacryloxy)propyl trimethoxysilane; taking cephalexin (CFX) as a template molecule, methacrylic acid (MAA) as a functional monomer, ethylene alcohol dimethacrylate (EGDMA) and N, N- methylene bisacrylamide (BIS) as a crosslinking agent, and cetane as a porogenic diluent and an organic solvent to prepare a magnetic carbon microsphere surface imprinted adsorbent. The magnetic carbon microsphere surface imprinted adsorbent material prepared by the method disclosed by the invention is low in cost and simple in preparation, and has high recognition, high selectivity, and high separation enrichment capacity on target molecules, and a high absorption speed.
Description
Technical field
The present invention relates to a kind of preparation method of magnetic carbon microsphere surface cefalexin molecular engram sorbing material, belong to technical field of environment function material preparation.
Background technology
Cefalexin antibiotic belongs to Beta-lactam medicine, has the advantages such as has a broad antifungal spectrum, antibacterial action are strong, penicillin resistant enzyme.Be usually used in treating septicemia, meningitis endocarditis etc. in livestock-raising.Irrational use causes these medicines to accumulate in animal derived tissue.There is allergic reaction after eating these animal derived foods in people, even suffers a shock, and constitutes serious threat to human health.The abuse of high amount of drug, also can cause the generation of antibody-resistant bacterium, destroys ecological environment.How to be separated these medicament residues and to have become problem demanding prompt solution, particularly research and develop a kind of isolation technics quick, sensitive, simple to operate and product is very important.
Molecularly imprinted polymer is polymer target molecule (template molecule) to specific recognition and selective absorption synthesized by molecular imprinting.Surface molecule print technology is by being based upon molecular recognition site on the surface of host material, well solve that the highly cross-linked template molecule caused of conventional bulk polymerization can not be removed completely, the little and mass transfer of binding ability is slow, avtive spot embedded deeply, the shortcomings such as the dynamic performance of adsorption-desorption is not good.
In recent years, utilize intelligent trace system to prepare focus that the intellectual material that can produce respective action to magnetic field, temperature, light source and pH value becomes research.Preparing temperature sensitive type imprinted polymer material with NIPA (NIPAm) for temperature sensitive structures alone is a kind of typical intelligent trace system, and the introducing of temperature-sensing property makes Temperature-sensitive Molecular Imprinted Polymers can variation with temperature and changing to the Selective recognition ability of template molecule.In addition ferriferrous oxide nano-particle is due to stronger superparamagnetism, be used to the magnetic surface imprinted polymeric materials preparing nucleocapsid structure, utilize the superparamagnetism of ferriferrous oxide nano-particle matrix and the specific adsorption effect of clad imprinted polymeric materials, magnetic surface imprinted polymeric materials can realize optionally being separated rapidly with mother liquor by target contaminant under outside magnetic field is assisted.But, in preparation technology, because ferriferrous oxide nano-particle can be reunited and the magnetic blotting polymeric material formed can exist the problem of leakage field.
This method is that carbon source prepares magnetic carbon microballoon with walnut shell, utilize solvent thermal reaction by immobilized for ferriferrous oxide nano-particle carbosphere surface of preparing at pomelo peel, carry out trace polymerization process at its composite material surface subsequently, well solve the leakage field of magnetic blotting polymeric material and the problem of ferriferrous oxide nano-particle reunion.This preparation method not yet has report at present.
Summary of the invention
The invention provides that a kind of cost is low, preparation method be simple, have target molecule highly to identify, high selectivity and high score from accumulation ability and fast magnetic carbon microsphere surface molecular engram sorbing material of adsorption rate and preparation method thereof, target molecule is cefalexin molecule.
The technical solution used in the present invention is: the present invention is that carbon source prepares magnetic carbon microballoon with walnut shell, and carries out ethene functional modification with 3-(methacryloxypropyl) propyl trimethoxy silicane to magnetic carbon microsphere surface.Refer in particular to the stabilizing agent using the magnetic carbon microballoon of vinyl functionalization as Pickering emulsion, cefalexin (CFX) is as template molecule, methacrylic acid (MAA) is function monomer, ethylene glycol dimethacrylate (EGDMA) and N, N-methylene-bisacrylamide (BIS) is as crosslinking agent, hexadecane, as perforating agent and organic solvent, mixes as oil phase.Magnetic carbon microballoon and 2,2-azo two (the 2-methyl-propyl miaow) dihydrochloride (APPH) of vinyl functionalization are added to the water, as aqueous phase after dispersion.Mixed with oil phase by aqueous phase, ultrasonic preparation becomes stable Pickering emulsion.Then carry out Pickering emulsion polymerisation, be prepared into magnetic carbon microsphere surface trace adsorbent.Subsequently, template molecule is washed away with the mixed liquor that methyl alcohol and acetic acid are 9: 1 (V/V), 50-60 DEG C of vacuum drying.Finally, the magnetic carbon microsphere surface trace adsorbent Selective recognition that is used for cefalexin in water environment be separated.
The method of magnetic carbon microsphere surface trace adsorbent is prepared in emulsion polymerisation, carries out according to following step:
(1) preparation of magnetic carbon microballoon
Choosing walnut shell at the temperature of 115 DEG C dries 18h, by above-mentioned oven dry walnut shell powder be broken to particle diameter at about 2.0-4.0mm, obtain feed particles.By the hydrochloric acid of above-mentioned walnut shell particle by 3.0mol/L, reflux 10-15h at 60-70 DEG C, is repeatedly worth neutrality, dries to constant weight, obtain acid activation walnut shell particle at being placed in 50-60 DEG C with distilled water washing.
By the acid activation walnut shell particle of above-mentioned preparation and FeCl
3.6H
2o, sodium acetate are according to acid activation walnut capsomere: FeCl
3.6H
2o: sodium acetate is (0.6-1.0): (0.3-0.5): the ratio of (1.5-2.0) (g/g/g) is dissolved in ethylene glycol, the addition of ethylene glycol is according to acid activation walnut capsomere: ethylene glycol=1.0: (90-100) (g/ml), ultrasonic agitation 30-60min, mix, polyethylene glycol is added subsequently in above-mentioned mixed liquor, the addition of polyethylene glycol is according to acid activation walnut capsomere: polyethylene glycol=1.0: (1.5-1.8) (g/g), magnetic agitation 30-60min, after stirring terminates, mixed liquor proceeds to water-bath still Program and heats up, 3-5h rises to 150-200 DEG C, this thermotonus 8.0-10h, product ethanol and distilled water wash repeatedly, be dried to constant weight, obtain magnetic carbon microballoon.
(2) functional magnetic carbosphere preparation
According to magnetic carbon microballoon: 3-(methacryloxypropyl) propyl trimethoxy silicane: toluene amount ratio is 1.0: (3.0-4.0): (90-100) (g/g/g) adds in there-necked flask, 300-400rpm mechanical agitation 20-24h at 70-90 DEG C, a large amount of toluene wash does not participate in 3-(methacryloxypropyl) propyl trimethoxy silicane of reaction with removing, 60 DEG C of vacuum drying, namely obtain the magnetic carbon microballoon of vinyl functionalization.
(3) magnetic carbon microsphere surface trace adsorbent is prepared in emulsion polymerisation
By cefalexin, methacrylic acid (MAA) and hexadecane according to 1: (5-7): the ratio mixing of (5: 8) (mmol/mmol/m1), after ultrasonic 10-15min, sealing is preserved, pre-assembled 10-14h.Subsequently in above-mentioned mixed liquor according to mol ratio cefalexin: ethylene glycol dimethacrylate (EGDMA): N, N-methylene-bisacrylamide (BIS) is 1: (20-30): the ratio of (1.5-1.8) (mmol/mmol/mmol) adds ethylene glycol dimethacrylate (EGDMA) and N, N-methylene-bisacrylamide (BIS), then by the magnetic carbon microballoon of above-mentioned functions, 2, 2-azo two (2-methyl-propyl miaow) dihydrochloride (APPH) and water mixing, the magnetic carbon microballoon ratio wherein controlling cefalexin and functionalization is 1: (0.8-1.2) (mmol/g), the ratio of cefalexin and water is 1: (50-100) (mol/ml), cefalexin and 2, 2-azo two (2-methyl-propyl miaow) dihydrochloride (APPH) is than being 1: (0.05-0.07) (mol/g), ultrasonic 20-30min is uniformly dispersed, aqueous phase is mixed with oil phase, ultrasonic 5-10min in ice bath, be prepared into stable Pickering emulsion.Subsequently, after the Pickering emulsion of preparation leads to nitrogen 10-20min, keep 18-24h at 60-70 DEG C.Products therefrom absolute ethyl alcohol and distilled water repeatedly wash, and finally wash away template molecule, last 50-60 DEG C vacuum drying with the mixed liquor that methyl alcohol and acetic acid are 9: 1 (V/V).The preparation method of magnetic carbon microsphere surface non-trace adsorbent is the same, does not just add cefalexin in process.
Accompanying drawing explanation
The isollaothermic chart of Fig. 1 magnetic carbon microsphere surface trace adsorbent and non-trace adsorbent cefalexin (CFX).As we know from the figure, adsorption capacity increases along with the rising of concentration thereupon.Trace adsorbent to the adsorption capacity of cefalexin (CFX) much larger than non-trace adsorbent to cefalexin (CFX) adsorption capacity, show good specific recognition performance, the avtive spot existing in trace adsorbent and match with cefalexin (CFX) molecule is described.
The dynamics figure of Fig. 2 magnetic carbon microsphere surface trace adsorbent and non-trace adsorbent cefalexin (CFX).As we know from the figure, originally, along with the increase of adsorption time, adsorption capacity increases sharply, after 30min, absorption reaches balance, in whole Longer absorption times, the adsorption capacity of trace adsorbent to cefalexin is greater than non-trace adsorbent to cefalexin adsorption capacity, shows good absorption property.
Fig. 3 magnetic carbon microsphere surface trace adsorbent and non-trace adsorbent cefalexin (CFX) with other the three kinds antibiotic experiments of competition, result shows, trace adsorbent demonstrates cefalexin good Selective recognition separation and concentration ability.
Detailed description of the invention
Below in conjunction with concrete embodiment, the invention will be further described.
Embodiment 1
(1) preparation of magnetic carbon microballoon
Choosing walnut shell at the temperature of 115 DEG C dries 18h, by above-mentioned oven dry walnut shell powder be broken to particle diameter at about 2.0-4.0mm, obtain feed particles.By the hydrochloric acid of above-mentioned walnut shell particle by 3.0mol/L, reflux 12h at 70 DEG C, is repeatedly worth neutrality, dries to constant weight, obtain acid activation walnut shell particle at being placed in 60 DEG C with distilled water washing.
By the acid activation walnut shell particle of above-mentioned preparation and FeCl
3.6H
2o, sodium acetate are according to acid activation walnut capsomere: FeCl
3.6H
2o: sodium acetate is that the ratio of 1.0: 0.5: 2.0 (g/g/g) is dissolved in ethylene glycol, the addition of ethylene glycol is according to acid activation walnut capsomere: ethylene glycol=1.0: 100 (g/ml), ultrasonic agitation 30min, mix, polyethylene glycol is added subsequently in above-mentioned mixed liquor, the addition of polyethylene glycol is according to acid activation walnut capsomere: polyethylene glycol=1.0: 1.6 (g/g), magnetic agitation 60min, after stirring terminates, mixed liquor proceeds to water-bath still Program and heats up, 4h rises to 200 DEG C, this thermotonus 10h, product ethanol and distilled water wash repeatedly, be dried to constant weight, obtain magnetic carbon microballoon.
(2) functional magnetic carbosphere preparation
According to magnetic carbon microballoon: 3-(methacryloxypropyl) propyl trimethoxy silicane: toluene amount ratio is that 1.0: 3.0: 100 (g/g/g) add in there-necked flask, 400rpm mechanical agitation 24h at 80 DEG C, a large amount of toluene wash does not participate in 3-(methacryloxypropyl) propyl trimethoxy silicane of reaction with removing, 60 DEG C of vacuum drying, namely obtain the magnetic carbon microballoon of vinyl functionalization.
(3) magnetic carbon microsphere surface trace adsorbent is prepared in emulsion polymerisation
Cefalexin, methacrylic acid (MAA) and the hexadecane ratio according to 1: 5: 8 (mmol/mmol/m1) mixed, after ultrasonic 15min, sealing is preserved, pre-assembled 12h.Subsequently in above-mentioned mixed liquor according to mol ratio cefalexin: ethylene glycol dimethacrylate (EGDMA): N, N-methylene-bisacrylamide (BIS) is that the ratio of 1: 20: 1.5 (mmol/mmol/mmol) adds ethylene glycol dimethacrylate (EGDMA) and N, N-methylene-bisacrylamide (BIS), then by the magnetic carbon microballoon of above-mentioned functions, 2, 2-azo two (2-methyl-propyl miaow) dihydrochloride (APPH) and water mixing, the magnetic carbon microballoon ratio wherein controlling cefalexin and functionalization is 1: 1.0 (mmol/g), the ratio of cefalexin and water is 1: 100 (mol/ml), cefalexin and 2, 2-azo two (2-methyl-propyl miaow) dihydrochloride (APPH) is than being 1: 0.05 (mol/g), ultrasonic 30min is uniformly dispersed, aqueous phase is mixed with oil phase, ultrasonic 10min in ice bath, be prepared into stable Pickering emulsion.Subsequently, after the Pickering emulsion of preparation leads to nitrogen 20min, keep 24h at 60 DEG C.Products therefrom absolute ethyl alcohol and distilled water repeatedly wash, and finally wash away template molecule with the mixed liquor that methyl alcohol and acetic acid are 9: 1 (V/V), last 60 DEG C of vacuum drying.The preparation method of magnetic carbon microsphere surface non-trace adsorbent is the same, does not just add cefalexin in process.
In the present invention, in specific embodiments, absorption property evaluation is carried out by the following method: utilize Static Adsorption to test.25ml cefalexin solution is added in centrifuge tube, respectively to wherein adding 10mg magnetic carbon microsphere surface trace adsorbent and non-trace adsorbent, static in water bath with thermostatic control, investigate initial concentration solution, time of contact to the impact of cefalexin adsorbance.Absorption reach balance after, supernatant Nd-Fe-B permanent magnet separated and collected, in solution not by adsorb cefalexin molecular concentration ultraviolet-uisible spectrophotometer record, calculate adsorption capacity (q)
q＝[(C
0-C
e)V]/W
C
0(μm ol/L) and C
e(μm ol/L) is respectively concentration during initial concentration and the balance of cefalexin, and V (mL) and W (mg) is respectively the consumption of liquor capacity and adsorbent.
Embodiment 2
Get 25ml initial concentration and be respectively 5, 10, 20, 30, 50, 60, 80, 100, 150, 200, the cefalexin solution of 300 μm of ol/L joins in centrifuge tube, add 10mg magnetic carbon microsphere surface trace adsorbent and non-trace adsorbent respectively, test solution is placed in 25 DEG C of water-baths and leaves standstill 24.0h, supernatant Nd-Fe-B permanent magnet separated and collected, do not measured by the cefalexin molecular concentration ultraviolet-uisible spectrophotometer adsorbed, calculate adsorption capacity, show shown in Fig. 1, the saturated adsorption capacity of trace adsorbent is the 19.36umol/g of 52.35umol/g higher than non-trace sorbing material, prove that trace sorbing material exists a large amount of trace holes, demonstrate good imprinting effect.
Embodiment 3
Getting 25ml initial concentration is that the cefalexin solution of 150 μm of ol/L joins in centrifuge tube, add 10mg magnetic carbon microsphere surface trace adsorbent and non-trace adsorbent, test solution is placed in 25 DEG C of water-baths and leaves standstill 2 respectively, 5, 10, 20, 30, 45, 60, 90, 120 and 150min, after having left standstill, supernatant Nd-Fe-B permanent magnet separated and collected, do not measured by the cefalexin molecular concentration ultraviolet-uisible spectrophotometer adsorbed, calculate adsorption capacity, as can be known from Fig. 2, originally, along with the increase of adsorption time, adsorption capacity increases sharply, after 30min, absorption reaches balance, in whole Longer absorption times, the adsorption capacity of magnetic carbon microsphere surface trace adsorbent to cefalexin molecule is greater than non-trace adsorbent to cefalexin Molecular Adsorption capacity, show good absorption property.
Embodiment 4
Select tetracycline (TC), antibiotic that sulphadiazine (SD) and ampicillin (AMP) are competitive Adsorption.Obtain solution concentration is 100 μm of above-mentioned three kinds of antibiotic of ol/L respectively.Getting the solution that 25ml configures adds in centrifuge tube, adds 10mg magnetic carbon microsphere surface trace adsorbent and non-trace adsorbent respectively, test solution is placed in 25 DEG C of water-baths and leaves standstill 12.0h.Adsorb saturated after, supernatant Nd-Fe-B permanent magnet separated and collected, do not measured by the various competitive Adsorption antibiotic concentration ultraviolet-uisible spectrophotometers adsorbed, calculate adsorption capacity, as can be seen from Figure 3, trace adsorbent has significant specific recognition to CFX, and adsorption capacity is apparently higher than other antibiotic.
Claims (10)
1. a preparation method for magnetic carbon microsphere surface cefalexin molecular engram sorbing material, is characterized in that carrying out according to following step:
(1) preparation of magnetic carbon microballoon
Choosing walnut shell at the temperature of 115 DEG C dries 18h, by above-mentioned oven dry walnut shell powder be broken to particle diameter at about 2.0-4.0mm, obtain feed particles.By the hydrochloric acid of above-mentioned walnut shell particle by 3.0mol/L, reflux 10-15h at 60-70 DEG C, is repeatedly worth neutrality, dries to constant weight, obtain acid activation walnut shell particle at being placed in 50-60 DEG C with distilled water washing;
By the acid activation walnut shell particle of above-mentioned preparation and FeCl
36H
2o, sodium acetate are dissolved in ethylene glycol, ultrasonic agitation 30-60min, mixes, and adds polyethylene glycol subsequently in above-mentioned mixed liquor, magnetic agitation 30-60min, after stirring terminates, mixed liquor proceeds to water-bath still Program and heats up, and 3-5h rises to 150-200 DEG C, this thermotonus 8.0-10h, product ethanol and distilled water wash repeatedly, are dried to constant weight, obtain magnetic carbon microballoon;
(2) functional magnetic carbosphere preparation
The mixed liquor of the magnetic carbon microballoon of above-mentioned preparation, 3-(methacryloxypropyl) propyl trimethoxy silicane and toluene adds in there-necked flask in proportion, 300-400rpm mechanical agitation 20-24h at 70-90 DEG C, a large amount of toluene wash does not participate in 3-(methacryloxypropyl) propyl trimethoxy silicane of reaction with removing, 60 DEG C of vacuum drying, namely obtain the magnetic carbon microballoon of vinyl functionalization;
(3) magnetic carbon microsphere surface trace adsorbent is prepared in emulsion polymerisation
Cefalexin, methacrylic acid (MAA) and hexadecane mix in proportion, and after ultrasonic 10-15min, sealing is preserved, pre-assembled 10-14h.Subsequently by ethylene glycol dimethacrylate (EGDMA) and N, N-methylene-bisacrylamide (BIS), add in above-mentioned pre-polymer solution, then by the magnetic carbon microballoon, 2 of above-mentioned functions, 2-azo two (2-methyl-propyl miaow) dihydrochloride (APPH) and water mixing, ultrasonic 20-30min is uniformly dispersed, and is mixed by aqueous phase with oil phase, ultrasonic 5-10min in ice bath, is prepared into stable Pickering emulsion.Subsequently, after the Pickering emulsion of preparation leads to nitrogen 10-20min, keep 18-24h at 60-70 DEG C.Products therefrom absolute ethyl alcohol and distilled water repeatedly wash, and finally wash away template molecule, last 50-60 DEG C vacuum drying with the mixed liquor that methyl alcohol and acetic acid are 9: 1 (VN).
2. the method for magnetic carbon microsphere surface trace adsorbent is prepared in emulsion polymerisation according to claim 1, it is characterized in that acid activation walnut capsomere: FeCl in step (1)
36H
2o: sodium acetate is (0.6-1.0): (0.3-0.5): (1.5-2.0) (g/g/g), the addition of ethylene glycol is according to acid activation walnut capsomere: ethylene glycol=1.0: (90-100) (g/ml), and the addition of polyethylene glycol is according to acid activation walnut capsomere: polyethylene glycol=1.0: (1.5-1.8) (g/g).
3. the method for magnetic carbon microsphere surface trace adsorbent is prepared in emulsion polymerisation according to claim 1, it is characterized in that magnetic carbon microballoon: 3-(methacryloxypropyl) propyl trimethoxy silicane in step (2): toluene mass ratio is 1.0: (3.0-4.0): (90-100) (g/g/g).
4. the method for magnetic carbon microsphere surface trace adsorbent is prepared in emulsion polymerisation according to claim 1, it is characterized in that the ratio 1 of the cefalexin described in step (3), methacrylic acid (MAA) and hexadecane: (5-7): (5: 8) (mmol/mmol/ml).
5. the method for magnetic carbon microsphere surface trace adsorbent is prepared in emulsion polymerisation according to claim 1, it is characterized in that the cefalexin described in step (3), ethylene glycol dimethacrylate (EGDMA) and N, N-methylene-bisacrylamide (BIS) ratio are 1: (20-30): (1.5-1.8) (mmol/mmol/mmol).
6. the method for magnetic carbon microsphere surface trace adsorbent is prepared in emulsion polymerisation according to claim 1, it is characterized in that the magnetic carbon microballoon ratio of the cefalexin described in step (3) and functionalization is 1: (0.8-1.2) (mmol/g).
7. the method for magnetic carbon microsphere surface trace adsorbent is prepared in emulsion polymerisation according to claim 1, it is characterized in that the ratio of the cefalexin described in step (3) and water is 1: (50-100) (mol/ml).
8. the method for magnetic carbon microsphere surface trace adsorbent is prepared in emulsion polymerisation according to claim 1, it is characterized in that the cefalexin described in step (3) and 2,2-azo two (2-methyl-propyl miaow) dihydrochloride (APPH) than being 1: (0.05-0.07) (mol/g).
9. according to the magnetic carbon microsphere surface cefalexin molecular engram sorbing material that the preparation method of any one of claim 1-8 prepares.
10. magnetic carbon microsphere surface chloramphenicol molecular imprinting sorbing material according to claim 9 is used for identification and the enrichment of cefalexin molecule.
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| CN110339823A (en) * | 2019-07-01 | 2019-10-18 | 河南城建学院 | A kind of Eichhornia crassipes base magnetism multi-stage porous carbon surface imprinted material and its preparation method and application |
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