CN109939656A - The preparation method and application of the magnetic molecularly imprinted nanoparticle of Norfloxacin - Google Patents
The preparation method and application of the magnetic molecularly imprinted nanoparticle of Norfloxacin Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of the magnetic molecularly imprinted nanoparticle of Norfloxacin, include the following steps: that ferric chloride hexahydrate 1) is dissolved in water, deoxygenation, stirring, addition Iron dichloride tetrahydrate, sodium hydroxide solution heating are reacted, and A substance is obtained；2) A substance is reacted in ethanol-water solution with 3- aminopropyl triethoxysilane, obtains surface amino groups silanization ferriferrous oxide nano-particle；3) surface amino groups silanization ferriferrous oxide nano-particle, Norfloxacin, dopamine are added in ethanol-water solution and are reacted, obtain B substance；4) B substance is first washed with Ethanol-Acetic Acid solution, is washed with water and washs, be dried in vacuo, obtain the magnetic molecularly imprinted nanoparticle of Norfloxacin.This method can effectively improve the superparamagnetism and selectivity of target nanoparticle.The invention also discloses the magnetic molecularly imprinted nanoparticle of the Norfloxacin as made from this method and its applications in the detection and separation of Norfloxacin.
Description
Technical field
The present invention relates to food analysis functional material preparation fields, and in particular to a kind of Norfloxacin magnetic molecule print
The preparation method of mark nanoparticle.The invention further relates to a kind of magnetic molecularly imprinted nanometers of Norfloxacin as made from this method
Particle and its application in the enrichment of Norfloxacin molecule and detection.
Background technique
Norfloxacin is third generation Comprecin --- one kind has the fluoro- 7- piperazine -4- promise ketone ring structure of 6-
Extensive pedigree antibiotic is typically applied to the A subunit of DNA of bacteria helicase, inhibit DNA synthesis and duplication and generate antibacterial work
With.Relative to the first and second generation Comprecin, the antimicrobial spectrum further expansion of third generation quinolones, to staphylococcus
Equal gram-positive bacterias also have antibacterial action, then further strengthen to the antibacterial action of some Gram-negative bacterias, raise in milk animal
It supports and is widely used in industry.The Norfloxacin of asian treatment concentration is often used as forage feed milk animal, to promote to grow,
It reduces dead.The improper use of Norfloxacin, which will lead to, Determination of norfloxacin residue in the dairy products sold in the market, long-term to take in
Human body drug resistance, development toxicity are not only resulted in, causes three-induced effect (carcinogenic, teratogenesis, mutagenesis), can also bring ecology to environment
The problems such as endangering.Therefore, it is husky with promise fluorine remaining in selectively concentration and separation environment or food that effective processing means are established
Star class antibiotic is extremely urgent.
Using molecular imprinting technology synthesis molecularly imprinted polymer (Molecular Imprinted Polymers,
MIPs host-guest coordination compound usually) is formed in conjunction with the covalent bond or non-covalent bond between function monomer using template molecule, then
The stereochemical structure that cladding complex is formed with the polymerization of crosslinking agent forms molecular engram after template molecule is dissociated in elution
Hole can carry out specific recognition and absorption to template molecule.Magnetism molecule imprinted polymer (Magnetic Molecular
Imprinted Polymers, MMIPs) it is using magnetic nanometer as carrier, by molecular imprinting technology in magnetic nanoparticle
Sublist face forms one layer of molecular engram layer for having molecular engram hole.Magnetism molecule trace nanoparticle have preparation it is simple, at
The advantages that this is cheap, reusable, can fast and effeciently identify and concentration and separation object under the action of an external magnetic field.So
And magnetic molecularly imprinted polymer is applied to the detection of the Comprecins such as Norfloxacin or separation is rarely reported,
Some Norfloxacin magnetic molecularly imprinted polymer sizes are larger, and preparation method is complicated, time-consuming, at high cost, to environment dirt
Dye is serious.
Summary of the invention
The purpose of the invention is to overcome Norfloxacin magnetic molecularly imprinted polymer size of the existing technology compared with
Greatly, preparation method complexity, at high cost, the serious problem of environmental pollution, provide a kind of magnetic molecularly imprinted nanometer of Norfloxacin
The preparation method of particle, have the advantages that preparation method it is simple, it is at low cost, be conducive to industrialization promotion.The present invention also provides one
Plant the magnetic molecularly imprinted nanoparticle of the Norfloxacin as made from this method and its in Norfloxacin detection or concentration and separation
Application, the nanoparticle have higher superparamagnetism and the selectivity to Norfloxacin molecule, to Norfloxacin have more
High concentration and separation effect, effectively improves the detection sensitivity to Norfloxacin.
To achieve the goals above, first aspect present invention provides a kind of magnetic molecularly imprinted nanoparticle of Norfloxacin
Preparation method includes the following steps: that ferric chloride hexahydrate 1) is dissolved in water, deoxygenation, stirring, addition Iron dichloride tetrahydrate, hydrogen
Sodium hydroxide solution heating is reacted, and is separated and collected to obtain A substance with magnetic utensil, stand-by after vacuum drying after being washed with water；
2) it by A substance after tetramethylammonium hydroxide activates, reacts, obtains in ethanol-water solution with 3- aminopropyl triethoxysilane
To surface amino groups silanization ferriferrous oxide nano-particle (Fe3O4@NH2NPs)；3) by surface amino groups silanization ferroso-ferric oxide
Nanoparticle, Norfloxacin, dopamine, which are added in ethanol-water solution, to be reacted, and is separated and collected to obtain B object with magnetic utensil
Matter；4) B substance is first washed with Ethanol-Acetic Acid solution, is washed with water and washs, be dried in vacuo, obtain Norfloxacin magnetic molecule print
Mark nanoparticle (MMIPs NPs).
Preferably, in the step 1), in every 100mL water, ferric chloride hexahydrate 4.5-5.5g is added, after dissolution,
The sodium hydroxide solution 37.5-42.5mL of Iron dichloride tetrahydrate 1.5-2.5g, 2mol/L is added.
Further, in the step 1), deoxygenation is carried out in the method for being passed through nitrogen；With 500-600 revs/min turn
Speed is stirred；The temperature of heating is 75-85 DEG C；Reaction time 0.5-1.5 hour；After reaction, it is received after being cooled to room temperature
Collect A substance；The magnetism utensil is neodymium iron boron strong magnet；The mode of washing is supersound washing, true after washing to pH value 7-7.5
Sky is dry.
Preferably, in the step 2), the volume ratio of water and ethyl alcohol is 1:1 in the ethanol-water solution, every
A substance 0.5-1g, 3- aminopropyl triethoxysilane 2-5mL is added in ethanol-water solution described in 120mL.
Further, in the step 2), the condition of the reaction are as follows: 30-60 DEG C of temperature, with 300-400 revs/min
Revolving speed be stirred, reaction time 7-12 hour.
Preferably, in the step 3), the volume ratio of water and ethyl alcohol is 1:1 in the ethanol water, in every 100mL
Norfloxacin 0.012-0.018g, dopamine 0.1-0.2g, the surface amino groups silanization are added in the ethanol water
Fe3O4Nanoparticle 0.3-0.75g.
Further, in the step 3), the condition of the reaction are as follows: 20-30 DEG C of temperature, with 250-350 revs/min
Revolving speed be stirred, reaction time 1-3 hour；The magnetism utensil is neodymium iron boron strong magnet.
Preferably, in the step 4), the volume ratio of ethyl alcohol and acetic acid is (95:5)-in the Ethanol-Acetic Acid solution
(98:2)；Described washed with Ethanol-Acetic Acid solution with the mode of washing being washed with water is supersound washing.
Second aspect of the present invention provides a kind of magnetic molecularly imprinted nanoparticle of Norfloxacin, which passes through this hair
The preparation method of the magnetic molecularly imprinted nanoparticle of Norfloxacin described in bright first aspect is made.
Third aspect present invention provide a kind of magnetic molecularly imprinted nanoparticle of Norfloxacin in the detection of Norfloxacin or
Application in concentration and separation.Specifically, the selection using the magnetic molecularly imprinted nanoparticle of Norfloxacin to Norfloxacin molecule
Property, the combination of realization and Norfloxacin molecule realizes its separation using its superparamagnetism, realizes the concentration and separation of Norfloxacin.
The concentration of Norfloxacin after the magnetic molecularly imprinted nanoparticle selective absorption of Norfloxacin is improved significantly, detection it is quick
Perception is greatly improved.
Through the above technical solutions, the preparation method of the magnetic molecularly imprinted nanoparticle of Norfloxacin of the invention, utilizes
The most common reagent is mixed and is reacted with molysite, using Norfloxacin as template molecule, by optimization processing, to prepare Norfloxacin
Magnetic molecularly imprinted nanoparticle, using the characteristic of oxidable auto polymerization in dopamine at room temperature weak basic condition, without making
With other poisonous and harmful reagents, environmental pollution is reduced.And existing Norfloxacin magnetic molecularly imprinted polymer preparation side
It is needed in method using function monomer MAA (methacrylic acid), crosslinking agent EGDMA (ethylene glycol dimethacrylate), initiator
The poisonous and harmful reagent such as AIBN (azodiisobutyronitrile) and solvent such as methanol and acetonitrile, to the seriously polluted of environment.Surface amino groups
Silanization Fe3O4The synthesis of nanoparticle uses coprecipitation, the surface amino groups silanization Fe of synthesis3O4Nanoparticle it is pure and
Have certain dimensional controllability, intergranular reunion is reduced by electrostatic repulsion between particle, increases dispersibility.Entire mistake
Journey is easy to operate, the time is short, at low cost, small to environmental hazard, is convenient for industrialization promotion.Norfloxacin magnetic molecule of the invention
Trace nanoparticle, size are only 14.06nm, have good superparamagnetism and the selectivity to Norfloxacin, are more suitable for
Magnetite gathering separation is carried out to Norfloxacin in complicated food substrate.Product of the invention improves the richness to Norfloxacin
Collect separative efficiency, can be detected directly or after eluting using analysis and detecting instrument, the sensibility of detection can be effectively improved,
Play the role of shortening analysis time, improves analysis efficiency.
Detailed description of the invention
Fig. 1 is the obtained Fe of one embodiment of the present of invention3O4NPs (ferriferrous oxide nano-particle), Fe3O4@
NH2The transmission electron microscope picture of NPs, MMIPs NPs；
Fig. 2 is the obtained Fe of one embodiment of the present of invention3O4NPs、Fe3O4@NH2The Fourier of NPs, MMIPs NPs
Infrared spectrogram；
Fig. 3 is the obtained Fe of one embodiment of the present of invention3O4NPs、Fe3O4@NH2The vibration sample of NPs, MMIPs NPs
Product magnetometer map；
Fig. 4 is that the MMIPs NPs and MNIPs NPs (magnetic non-molecular imprinting nano particles) of one embodiment of the invention is right
The Norfloxacin adsorption capacity comparative diagram of various concentration；
Fig. 5 is the curve of adsorption kinetics of MMIPs NPs and MNIPs NPs to Norfloxacin of one embodiment of the invention
Comparative diagram；
Fig. 6 is that the MMIPs NPs and MNIPs NPs of one embodiment of the invention are special to the absorption of some Common Antibiotics
Specific control figure.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
Below in conjunction with attached drawing to the specific reality of the preparation method of the magnetic molecularly imprinted nanoparticle of Norfloxacin of the invention
The mode of applying is described in detail, it should be appreciated that the specific embodiments described herein are only used for describing and explaining this hair
Bright, protection scope of the present invention is not limited to following specific embodiments.
In a specific embodiment of the invention, used transmission electron microscope is the model of FEI Co., U.S. production
The transmission electron microscope of Tecnai G20；Fourier infrared spectrograph is Japanese Shimadzu Corporation's production, model IRAffinity-1；Vibration
Dynamic sample magnetometer is the production of U.S. Quantum Design company, model MPMS-XL-7；Ultraviolet-uisible spectrophotometer is
Japanese Shimadzu Corporation's production, model UV-2450.Norfloxacin is purchased from Shanghai Yuan Ye Biotechnology Co., Ltd；Dopamine, four
Ammonium hydroxide and 3- aminopropyl triethoxysilane are purchased from Shanghai Jing Chun biochemical technology limited liability company；It is used
Water is secondary distilled water, deionized water or osmosis filtration water；Other reagents are commercially available.Heretofore described magnetic device
Tool can be various permanent magnets, electromagnetism iron product, use neodymium iron boron strong magnet in a specific embodiment of the invention.
In a specific embodiment of the invention, absorption property evaluation carries out by the following method: real using Static Adsorption
Test completion.The Norfloxacin solution of 1mL various concentration (0.02-0.1mg/mL) is added in centrifuge tube, is added thereto respectively
Enter 4mg MMIPs NPs or 4mg MNIPs NPs, stood in water bath with thermostatic control, after absorption reaches saturation, is received by Magnetic Isolation
Collection, obtains clear liquid at the middle and upper levels, Norfloxacin molecular concentration unadsorbed in test solution is measured with ultraviolet-uisible spectrophotometer, counts
Calculation obtains adsorption capacity Q and adsorption efficiency ω.
In formula, CoIt is the initial concentration (mg/mL) of Norfloxacin, Cs is the concentration (mg/mL) of Norfloxacin in supernatant,
V is the volume (mL) of solution, and m is the quality (g) of MMIPs NPs or MNIPs NPs.
It is husky to the preparation method of the magnetic molecularly imprinted nanoparticle of Norfloxacin of the invention, promise fluorine by the following examples
The magnetic molecularly imprinted nanoparticle of star and its application are described in detail.
Embodiment 1
1) after 5g ferric chloride hexahydrate being dissolved in 100mL water, nitrogen is passed through to remove the oxygen in solution；Tetra- water of 2g is added
Frerrous chloride, 40mL concentration are closed as 2mol/L sodium hydroxide solution, is stirred with 550 revs/min of revolving speed, in 80 DEG C of temperature
It is reacted under the conditions of degree, the reaction time 1 hour.Solution is cooled to room temperature after reaction, is collected with neodymium iron boron strong magnet
Magnetisable material A substance in solution；A substance is cleaned by ultrasonic with water, is repeated several times, until the pH of cleaning solution is 7；Vacuum
It is dry.
2) it weighs the A material solid that 0.8g step 1) obtains and the second of 120mL is added after tetramethylammonium hydroxide activates
The volume ratio of alcohol and water is 3mL 3- aminopropyl triethoxysilane to be added, with 350 revs/min in the ethanol water of 1:1
Revolving speed stirring, temperature be 40 DEG C under conditions of react 10 hours, be made Fe3O4@NH2NPs。
3) by 0.5g Fe3O4@NH2NPs be dissolved in the second alcohol and water of 100mL volume ratio be 1:1 ethanol water (wherein
Contain 100mmol/LTris-HCl, pH=8.5) in, 0.015g Norfloxacin, 0.14g dopamine is added, with 300 revs/min
Revolving speed stirring, reacted 2 hours under the conditions of 25 DEG C of temperature.It collects to obtain B substance using neodymium iron boron strong magnet concentration and separation.
4) supersound washing of Ethanol-Acetic Acid solution 6 times for being 97:3 by the volume ratio of B substance ethyl alcohol and acetic acid, then use water
Supersound washing 2 times, vacuum drying obtains MMIPs NPs.
Embodiment 2
1) after 4.5g ferric chloride hexahydrate being dissolved in 100mL water, nitrogen is passed through to remove the oxygen in solution；1.5g is added
Iron dichloride tetrahydrate, 37.5mL concentration are 2mol/L sodium hydroxide solution, are stirred with 500 revs/min of revolving speed, 75
DEG C temperature under the conditions of reacted, the reaction time 0.5 hour.Solution is cooled to room temperature after reaction, it is strong with neodymium iron boron
Magnet collects the magnetisable material A substance in solution；A substance is cleaned by ultrasonic with water, is repeated several times, until the pH of cleaning solution
It is 7；Vacuum drying.
2) it weighs the A material solid that 0.5g step 1) obtains and the second of 120mL is added after tetramethylammonium hydroxide activates
The volume ratio of alcohol and water is 2mL 3- aminopropyl triethoxysilane to be added, with 300 revs/min in the ethanol water of 1:1
Revolving speed stirring, temperature be 30 DEG C under conditions of react 7 hours, with neodymium iron boron strong magnet collect solution in magnetisable material,
That is surface amino groups silanization ferriferrous oxide nano-particle (Fe3O4@NH2NPs)。
3) by 0.3gFe3O4@NH2NPs be dissolved in the second alcohol and water of 100mL volume ratio be 1:1 ethanol water (wherein
Contain 100mmol/LTris-HCl, pH=8.5) in, 0.012g Norfloxacin, 0.1g dopamine is added, with 250 revs/min
Revolving speed stirring, reacts 3 hours under the conditions of 20 DEG C of temperature.It collects to obtain B substance using neodymium iron boron strong magnet concentration and separation.
4) supersound washing of Ethanol-Acetic Acid solution 6 times for being 95:5 by the volume ratio of B substance ethyl alcohol and acetic acid, then use water
Supersound washing 2 times, vacuum drying obtains the magnetic molecularly imprinted nanoparticle of Norfloxacin (MMIPs NPs).
Embodiment 3
1) after 5.5g ferric chloride hexahydrate being dissolved in 100mL water, nitrogen is passed through to remove the oxygen in solution；2.5g is added
Iron dichloride tetrahydrate, 42.5mL concentration are 2mol/L sodium hydroxide solution, are stirred with 600 revs/min of revolving speed, 85
DEG C temperature under the conditions of reacted, the reaction time 1.5 hours.Solution is cooled to room temperature after reaction, it is strong with neodymium iron boron
Magnet collects the magnetisable material A substance in solution；A substance is cleaned by ultrasonic with water, is repeated several times, until the pH of cleaning solution
It is 7.5；Vacuum drying.
2) it weighs the A material solid that 1g step 1) obtains and the ethyl alcohol of 120mL is added after tetramethylammonium hydroxide activates
Volume ratio with water is 5mL 3- aminopropyl triethoxysilane to be added, with 400 revs/min in the ethanol water of 1:1
Revolving speed stirring, reacts 12 hours under conditions of temperature is 60 DEG C, and Fe is made3O4@NH2NPs。
3) by 0.75g Fe3O4@NH2NPs is dissolved in ethanol water (its that the volume ratio of the second alcohol and water of 100mL is 1:1
In contain 100mmol/LTris-HCl, pH=8.5) in, be added 0.018g Norfloxacin, 0.2g dopamine, with 350 revs/min
Revolving speed stirring, reacted 1 hour under the conditions of 30 DEG C of temperature.It collects to obtain B substance using neodymium iron boron strong magnet concentration and separation.
4) supersound washing of Ethanol-Acetic Acid solution 6 times for being 98:2 by the volume ratio of B substance ethyl alcohol and acetic acid, then use water
Supersound washing 2 times, vacuum drying obtains MMIPs NPs.
Reference examples 1
Preparation method similarly to Example 1 is taken, the difference is that being added without Norfloxacin in step 3) (makees template point
Son is used), finally obtain magnetic non-molecular imprinting nano particles (MNIPs NPs).
Reference examples 2
After 4.75g ferric chloride hexahydrate is dissolved in 100mL water, nitrogen is passed through to remove the oxygen in solution；1.75g is added
Iron dichloride tetrahydrate, 39mL concentration are 2mol/L sodium hydroxide solution, are stirred with 525 revs/min of revolving speed, at 80 DEG C
It is reacted 1.5 hours under the conditions of temperature.It is collected to obtain ferriferrous oxide nano-particle (Fe with neodymium iron boron strong magnet3O4NPs, i.e. A object
Matter).
To preparing resulting Fe3O4NPs(a)、Fe3O4@NH2NPs (b), MMIPs NPs (c) carry out transmission electron microscope analysis, Fu
In leaf infrared spectrum analysis and vibrating specimen magnetometer analysis, analysis result it is as shown in Figure 1-Figure 3.
It will be seen from figure 1 that Fe3O4NPs (a) is mostly irregular cube shaped, and size is about 9.58nm；Fe3O4@NH2NPs
(b) monodispersity is presented, size is about 11.09nm, is illustrated using APTES success in Fe3O4NPs surface modification amino；
MMIPs NPs (c) rough surface, average grain diameter significantly increase, and size is about 14.06nm, this explanation is in Fe3O4@NH2The surface NPs
Form norfloxacin molecular imprinted film.
Figure it is seen that Fe3O4NPs (a) is in 559.35cm-1There is Fe-O characteristic absorption peak in place, 3365.78,
1627.92cm-1Place is then the stretching vibration due to caused by-OH and bending vibration absorption peak, 2372.44cm-1Place is due to air
In CO2Characteristic peak caused by caused C=O.Fe3O4@NH2NPs (b) is in about 570.92cm-1There is Fe-O characteristic absorption in place
There is Red Shift Phenomena and illustrates Fe in peak3O4@NH2NPs is relative to Fe3O4NPs (a) produces the variation of structure, it may be possible to amino silane
Change the introducing of decorative layer.In 1002.98 and 1109.06cm-1The absorption peak at place is the characteristic peak of Si-O-Si in APTES, is shown
APTES successfully modifies Fe3O4On.MMIPs NPs (c) is in about 570.92cm-1There is Fe-O characteristic absorption peak in place, red shift occurs
Phenomenon illustrates MMIPs NPs relative to Fe3O4NPs (a) produces the variation of structure, it may be possible to due to the introducing of molecular engram layer.
In 1265.30cm-1Absorption peak may be Norfloxacin and dopamine C-H in-plane bending vibration, the flexible vibration such as C-O, C-F
It is dynamic, and C -- C single bond skeletal vibration etc..1475.54cm-1Place is the skeletal vibration (σ C=C) of phenyl ring, and Norfloxacin and DOPA
Amine illustrates that molecular engram layer has been successfully introduced into Fe with the presence of phenyl ring3O4@NH2The surface NPs.
From figure 3, it can be seen that Fe3O4NPs(a)、Fe3O4@NH2NPs (b) and MMIPs NPs (c) without hysteresis,
Remanent magnetism and coercivity are zero, show that sample has superparamagnetism.Fe3O4NPs(a)、Fe3O4@NH2NPs (b) and MMIPs NPs
(c) saturation magnetization is respectively 51.03emu/g, 46.06emu/g and 38.58emu/g, and the reduction of the intensity of magnetization shows
Fe3O4The increase of surface reforming layer and imprinted layer reduces the magnetic susceptibility of magnetic iron ore, although as shown in figure 3, the magnetic of MMIPs NPs
Property decreases, but in the presence of an external magnetic field, still can be separated from solution by fast enriching.
It is as follows that absorption property evaluation is carried out to MMIPs NPs obtained by embodiment 1, embodiment 2 and embodiment 3:
Respectively take 1mL concentration be 0.1mg/mL Norfloxacin solution be added in centrifuge tube, be separately added into 4mg embodiment 1,
MMIPs NPs obtained by embodiment 2 and embodiment 3, by above-mentioned sample solution under 25 DEG C of constant temperatures, with 300 revs/min
Revolving speed shake 120 minutes, magnetic enrichment separates and collects supernatant liquor, unadsorbed Norfloxacin molecular concentration UV, visible light
Spectrophotometric determination, and adsorption capacity is calculated according to result.Obtained result such as table 1:
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Adsorption capacity Q (mg/g) | 14.672 | 12.505 | 13.810 |
The result shows that as to suction of the MMIPs NPs to Norfloxacin obtained by embodiment 1, embodiment 2 and embodiment 3
Attached capacity is close, wherein adsorption capacity highest of the MMIPs NPs as obtained by embodiment 1 to Norfloxacin.
It is as follows that adsorption experiment is carried out to MNIPs NPs made from MMIPs NPs as made from implementing 1, reference examples 1:
Experimental example 1
Take 1mL initial concentration be respectively 0.02mg/mL, 0.03mg/mL, 0.04mg/mL, 0.05mg/mL, 0.06mg/mL,
The Norfloxacin solution of 0.07mg/mL, 0.08mg/mL, 0.1mg/mL are added in centrifuge tube, are separately added into the system of 4mg embodiment 1
MNIPs NPs made from MMIPs NPs or the 4mg reference examples 1 obtained, by above-mentioned sample solution under 25 DEG C of constant temperatures, to turn
300 revs/min of speed shake 12 hours, and magnetic enrichment separates and collects supernatant liquor, unadsorbed blood concentration norfloxacin with it is ultraviolet can
See spectrophotometric determination, and adsorption capacity is calculated according to result.Such as Fig. 4 the result shows that, with the liter of blood concentration norfloxacin
Height, adsorption capacity are gradually increased, and are finally reached adsorption equilibrium, and under various concentration, and MMIPs NPs and MNIPs NPs are to promise fluorine
The adsorption curve variation of Sha Xing is consistent, but the adsorption capacity of MMIPs NPs is consistently greater than the adsorption capacity of MNIPs NPs, is reaching
When to adsorption equilibrium, it is MNIPs NPs to Norfloxacin that MMIPs NPs, which is 13.17mg/g to the adsorption capacity of Norfloxacin,
2.08 times of adsorption capacity (6.32mg/g) illustrate that MMIPs NPs has specific adsorption to Norfloxacin.
Experimental example 2
Taking 1mL concentration is that the Norfloxacin solution of 0.1mg/mL is added in centrifuge tube, is separately added into the system of 4mg embodiment 1
MNIPs NPs made from MMIPs NPs or the 4mg reference examples 1 obtained, by above-mentioned sample solution under 25 DEG C of constant temperatures, with 300
Rev/min revolving speed shake respectively 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, 60 minutes, 80 minutes, 100 points
Clock, 120 minutes, magnetic enrichment separate and collect supernatant liquor, and unadsorbed Norfloxacin molecular concentration is divided light with UV, visible light
Degree meter measurement, and adsorption capacity is calculated according to result.Such as Fig. 5 the result shows that, MMIPs NPs in first 40 minutes of adsorption process
Norfloxacin can be rapidly adsorbed with MNIPs NPs, the subsequent rate of adsorption slows down gradually, and finally reaches absorption at 60 minutes
Balance.MMIPs NPs is 14.17mg/g to the adsorption capacity of Norfloxacin, is adsorption capacity of the MNIPs NPs to Norfloxacin
2.21 times of (6.41mg/g) illustrate that MMIPs NPs has specific adsorption to Norfloxacin.
Experimental example 3
Taking 1mL Norfloxacin, Ciprofloxacin, sulphadiazine and tetracycline concentration is that the mixed solution of 0.02mg/mL adds
Enter into centrifuge tube, is separately added into MNIPs NPs made from MMIPs NPs or 4mg reference examples 1 made from 4mg embodiment 1, it will
Above-mentioned sample solution is under 25 DEG C of constant temperatures, after shaking 12 hours respectively with 300 revs/min of revolving speed, in Magneto separate collection
Layer clear liquid, unadsorbed Norfloxacin molecular concentration is measured with ultraviolet-uisible spectrophotometer, and calculates suction according to result
Attached efficiency.The result shows that being as shown in fig. 6,4mgMMIPs NPs is 100.12% to the adsorption efficiency of 0.02mg Norfloxacin
It is to 0.02mg Ciprofloxacin, sulphadiazine, 1.64 times of tetracycline adsorption efficiency, 14 times and 7.6 times；Ciprofloxacin is adsorbed
Efficiency is preferably since Norfloxacin is similar with Ciprofloxacin structure height.MNIPs NPs to the adsorption efficiency of Norfloxacin about
It is MMIPs NPs to the 1/2 of Norfloxacin adsorption efficiency, illustrates that MMIPs NPs has specific adsorption to Norfloxacin.
In conclusion the preparation method of the magnetic molecularly imprinted nanoparticle of Norfloxacin of the invention, used DOPA
Amine can aoxidize auto polymerization, not only can be used as function monomer, but also can be used as crosslinking agent, reduce the use of organic reagent.It uses
Ethanol water reduces processing cost as solvent, reduces existing Norfloxacin magnetic molecularly imprinted polymer preparation side
Pollution of the poisonous and harmful reagent to environment in method.The condition temperature needed for the reaction of magnetic nanometer surface synthetic molecules trace
With it is easy to operate, generated time only needs 1-3 hours, far below needed for existing Norfloxacin magnetic molecularly imprinted polymer
12-24 hours.Whole preparation process is easy to operate, at low cost, and pollution is few, is convenient for industrialization promotion.Norfloxacin of the invention
Magnetic molecularly imprinted nanoparticle, size are only 14.06nm, have good superparamagnetism, are had to Norfloxacin molecule good
Good selective absorption performance, and can be rapidly from solution by the complete adsorbing separation of magnet, supernatant clarification does not need again
Filtering.Concentration and separation process is easy, rapid.Thus, the magnetic molecularly imprinted nanoparticle of Norfloxacin of the invention can be preferably
Magnetite gathering separation is carried out to Norfloxacin, and can be detected directly or after eluting using analysis and detecting instrument, is improved
The sensibility and analysis efficiency of detection.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (10)
1. a kind of preparation method of the magnetic molecularly imprinted nanoparticle of Norfloxacin, which comprises the steps of:
1) ferric chloride hexahydrate is dissolved in water, Iron dichloride tetrahydrate is added in deoxygenation, stirring, sodium hydroxide solution heating carries out
Reaction, is separated and collected to obtain A substance with magnetic utensil, stand-by after vacuum drying after being washed with water；
2) anti-in ethanol-water solution with 3- aminopropyl triethoxysilane by A substance after tetramethylammonium hydroxide activates
It answers, obtains surface amino groups silanization ferriferrous oxide nano-particle；
3) surface amino groups silanization ferriferrous oxide nano-particle, Norfloxacin, dopamine are added in ethanol-water solution and are carried out
Reaction, separates and collects to obtain B substance with magnetic utensil；
4) B substance is first washed with Ethanol-Acetic Acid solution, is washed with water and washs, be dried in vacuo, obtain Norfloxacin magnetic molecule print
Mark nanoparticle.
2. the preparation method of the magnetic molecularly imprinted nanoparticle of Norfloxacin according to claim 1, which is characterized in that
In the step 1), in every 100mL water, ferric chloride hexahydrate 4.5-5.5g dissolution is added, Iron dichloride tetrahydrate is added
1.5-2.5g, the sodium hydroxide solution 37.5-42.5mL of 2mol/L.
3. the preparation method of the magnetic molecularly imprinted nanoparticle of Norfloxacin according to claim 2, which is characterized in that
In the step 1), deoxygenation is carried out in the method for being passed through nitrogen；The temperature of heating is 75-85 DEG C；With 500-600 revs/min
Revolving speed is stirred；Reaction time 0.5-1.5 hour；After reaction, A substance is collected after being cooled to room temperature；The magnetism device
Tool is neodymium iron boron strong magnet；The mode of washing is supersound washing, and washing to pH value is dried in vacuo after being 7-7.5.
4. the preparation method of the magnetic molecularly imprinted nanoparticle of Norfloxacin according to claim 1, which is characterized in that
In the step 2), the volume ratio of water and ethyl alcohol is 1:1, the ethanol-water solution described in every 120mL in the ethanol-water solution
It is middle that A substance 0.5-1g, 3- aminopropyl triethoxysilane 2-5mL is added.
5. the preparation method of the magnetic molecularly imprinted nanoparticle of Norfloxacin according to claim 4, which is characterized in that
In the step 2), the condition of the reaction are as follows: 30-60 DEG C of temperature, be stirred, reacted with 300-400 revs/min of revolving speed
Time 7-12 hour.
6. the preparation method of the magnetic molecularly imprinted nanoparticle of Norfloxacin according to claim 1, which is characterized in that
In the step 3), the volume ratio of water and ethyl alcohol is 1:1 in the ethanol water, in the ethanol water described in every 100mL
Norfloxacin 0.012-0.018g, dopamine 0.1-0.2g, the surface amino groups silanization Fe is added3O4Nanoparticle 0.3-
0.75g。
7. the preparation method of the magnetic molecularly imprinted nanoparticle of Norfloxacin according to claim 6, which is characterized in that
In the step 3), the condition of the reaction are as follows: 20-30 DEG C of temperature, be stirred, reacted with 250-350 revs/min of revolving speed
Time 1-3 hour；The magnetism utensil is neodymium iron boron strong magnet.
8. the preparation method of the magnetic molecularly imprinted nanoparticle of Norfloxacin according to claim 1, which is characterized in that
In the step 4), the volume ratio of ethyl alcohol and acetic acid is (95:5)-(98:2) in the Ethanol-Acetic Acid solution；It is described to use ethyl alcohol-
Acetic acid solution washing and the mode of washing being washed with water are supersound washing.
9. a kind of magnetic molecularly imprinted nanoparticle of Norfloxacin, which is characterized in that according to claim 1 described in any one of -7
The magnetic molecularly imprinted nanoparticle of Norfloxacin preparation method be made.
10. the magnetic molecularly imprinted nanoparticle of Norfloxacin as claimed in claim 9 is in the detection or concentration and separation of Norfloxacin
In application.
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