CN111269364B - Temperature response type aminoglycoside antibiotic imprinted magnetic nanoparticle based on polysaccharose and preparation method and application thereof - Google Patents
Temperature response type aminoglycoside antibiotic imprinted magnetic nanoparticle based on polysaccharose and preparation method and application thereof Download PDFInfo
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Abstract
A temperature response type aminoglycoside antibiotic imprinted magnetic nanoparticle based on polysaccharose and a preparation method and application thereof. Which comprises magnetic nano-particles and a polymeric monosaccharide temperature responsive layer attached to the surfaces of the magnetic nano-particles. The material is prepared by taking magnetic nanoparticles, template molecules, monosaccharide functional monomers and temperature response type monomers as main raw materials and adopting a surface imprinting method. The material takes magnetic nanoparticles as a matrix, a monosaccharide functional monomer and a temperature response type monomer (and an auxiliary monomer) are jointly applied to the preparation of the imprinting material, the imprinting material has excellent adsorption capacity and specificity recognition capacity on aminoglycoside antibiotics, the complete reversible capture and release of the aminoglycoside antibiotics in a water phase can be realized only by adjusting the temperature, the material has high repeated utilization degree, and the material has great advantages in the field of drug release or separation and enrichment in a complex biological matrix.
Description
Technical Field
The invention belongs to the field of environment response type materials, and particularly relates to a temperature response type aminoglycoside antibiotic imprinted magnetic nanoparticle based on monosaccharide and a preparation method and application thereof.
Background
Aminoglycoside antibiotics are an important antibiotic, have been widely applied to the field of livestock husbandry in China, and are often used as growth promoters to be added into feed. However, aminoglycoside antibiotics have ototoxicity, neurotoxicity, nephrotoxicity, allergy, and the like, with permanent irreversible ototoxicity being the most prominent. Therefore, it is important to develop materials capable of selectively capturing and releasing aminoglycoside antibiotics.
The molecular imprinting technology is widely applied to the fields of solid phase extraction, drug release and the like due to the advantages of easy preparation, high stability, specific recognition and the like. Currently, a few aminoglycoside antibiotic imprinted materials have been reported in the literature, but the working environment of the existing aminoglycoside antibiotic imprinted materials still depends on the traditional reversed-phase or reversed-phase/ion-exchange mixed chromatography mode, i.e. the elution step of the target analyte requires the use of a certain proportion of organic solvents or high-concentration salts. Elution solutions containing high concentrations of salts are incompatible with mass spectrometry systems and the harsh elution conditions cannot meet the in vivo or in vitro drug release application requirements.
In recent years, temperature-responsive molecularly imprinted materials have attracted great interest to researchers because they can capture and release template molecules by changing temperature. However, most temperature-responsive imprinted polymers cannot achieve complete release of target analytes only by adjusting the temperature due to non-specific adsorption between the temperature-responsive imprinted polymers and the target analytes, which greatly weakens the practical application value of such imprinted materials. According to the latest literature search, no temperature response type aminoglycoside antibiotic molecularly imprinted material has been reported so far.
Disclosure of Invention
In order to solve the technical problems, the invention provides an aminoglycoside antibiotic imprinted magnetic nanoparticle, which comprises a magnetic nanoparticle and a monosaccharide temperature-responsive polymer layer located on the outer surface of the magnetic nanoparticle.
According to the present invention, the monosaccharide temperature-responsive polymer layer may be selected from at least one of a polymer layer formed of a monosaccharide-based functional monomer and a temperature-responsive monomer, and/or a polymer layer formed of a monosaccharide-based functional monomer, a temperature-responsive monomer, and an auxiliary monomer.
Preferably, the monosaccharide functional monomer may be selected from monosaccharides functionalized with unsaturated bond-containing substituents (e.g., vinyl, allyl), for example, the vinyl-functionalized monosaccharide may be selected from at least one of glucose allyl amide, fructose allyl amide, arabinose allyl amide, and glucose allyl ester, etc.; illustratively selected from glucose allyl amides.
Preferably, the temperature-responsive monomer may be selected from at least one of N-alkylacrylamide-based temperature-responsive monomers, oligoethylene glycol-based temperature-responsive monomers, and vinylcaprolactam-based temperature-responsive monomers. For example, the temperature-responsive monomer may be selected from at least one of N-isopropylacrylamide, 2-methyl-2-propenoic acid-2- (2-methoxyethoxy) ethyl ester, and vinylcaprolactam.
Preferably, the auxiliary monomer may be selected from water-soluble vinyl monomers selected from at least one of vinylpyridine, acrylamide, p-vinylphenylboronic acid, dimethylaminoethyl methacrylate, and the like; for example, from acrylamide or dimethylaminoethyl methacrylate.
According to the invention, the average particle size range of the aminoglycoside antibiotic imprinted magnetic nanoparticles is 10-100 nm; for example, 10 to 20nm, 30 to 50nm, 60 to 90 nm.
Preferably, the thickness of the monosaccharide temperature-responsive polymer layer is not too thick and too thin, and too thick easily weakens the magnetism of the aminoglycoside antibiotic imprinted magnetic nanoparticles, so that the aminoglycoside antibiotic imprinted magnetic nanoparticles are not easy to recycle; if the thickness of the nanoparticle is too thin, the grafting amount of the polymer layer of the aminoglycoside antibiotic imprinted magnetic nanoparticle is affected, and the temperature response performance and the capturing amount of the aminoglycoside antibiotic are further affected.
According to the invention, the temperature response range of the aminoglycoside antibiotic imprinted magnetic nanoparticle is 10-60 ℃, for example 20-60 ℃.
The invention also provides a composition for preparing the aminoglycoside antibiotic imprinted magnetic nanoparticle, which comprises the following components in percentage by weight: magnetic nanoparticles, template molecules, monosaccharide functional monomers and temperature-responsive monomers.
According to the composition of the present invention, the magnetic nanoparticles, the template molecules, the monosaccharide functional monomers and the temperature-responsive monomers all have the definitions described above.
The composition according to the invention further comprises an auxiliary monomer, a cross-linking agent, a ligand and a transition metal salt.
According to the composition of the invention, the auxiliary monomer has the definition described above.
According to the composition, the mass ratio of the template molecule, the magnetic nanoparticles, the temperature-responsive monomer and the monosaccharide-based functional monomer can be (10-100): 1-80): 10-5000. For example, the mass ratio may be (20-80): (10-60): 10-1000), such as (40-60): (30-55): (50-500). Illustratively, the mass ratio is 20:20:51: 10.
According to the composition, the mass ratio of the magnetic nanoparticles, the auxiliary monomer, the cross-linking agent, the ligand and the transition metal salt can be (10-100): 0-5000): 1-100): 1. For example, the mass ratio may be (20-80): (0-1000): 2-1000): 5-50): 1, such as (40-60): 0-500): 5-100): 10-30): 1. Illustratively, the mass ratio is 20:0:2:1.245: 1.
According to the composition of the present invention, the template molecule may be selected from at least one of an aminoglycoside antibiotic, a sulfate thereof, and a compound comprising a substructure of the aminoglycoside antibiotic.
For example, the aminoglycoside antibiotic may be selected from at least one of neomycin, kanamycin, streptomycin, tobramycin, spectinomycin, gentamicin, sisomicin, micronomicin, amikacin, netilmicin, and the like; preferably, at least one selected from the group consisting of neomycin, kanamycin and streptomycin; illustratively, the aminoglycoside antibiotic is selected from streptomycin.
For example, the aminoglycoside antibiotic sulfate may be selected from at least one of neomycin sulfate, kanamycin sulfate, streptomycin sulfate, tobramycin sulfate, spectinomycin sulfate, gentamicin sulfate, sisomicin sulfate, micronomicin sulfate, amikacin sulfate, netilmicin sulfate, and the like; preferably, at least one selected from the group consisting of neomycin sulfate, kanamycin sulfate, and streptomycin sulfate; illustratively, the aminoglycoside antibiotic is selected from streptomycin sulfate.
For example, the compounds comprising a substructure of an aminoglycoside antibiotic are molecules comprising an amino cyclic alcohol and/or an amino sugar in the structure. For example, the compound comprising a substructure of an aminoglycoside antibiotic may be selected from at least one of aminocyclohexanol, aminocyclohexanol hydrochloride, and a monosaccharide (e.g., a six-carbon sugar); preferably selected from aminocyclohexanol, aminocyclohexanol hydrochloride or glucose.
According to the invention, the magnetic nanoparticles are optionally selected from all magnetic nanoparticles that are capable of further initiating or directly participating in radical polymerization.
For example, the magnetic nanoparticles capable of further initiating radical polymerization are selected from magnetic nanoparticles surface-modified with halogen groups, such as magnetic nanoparticles surface-modified with bromine groups, chlorine groups or fluorine groups.
For example, the magnetic nanoparticles directly participating in the radical polymerization are selected from carbon-carbon double bond surface modified magnetic nanoparticles, such as gamma-methacryloxypropyltrimethoxysilane surface modified magnetic nanoparticles.
According to the composition of the present invention, the cross-linking agent can be selected from water-soluble free radical polymerization cross-linking agents, for example, the cross-linking agent can be selected from at least one of N, N-dimethylene acrylamide, methylene bisacrylamide, ethylene glycol diacrylate, m-phenylene bismaleimide, pentaerythritol triacrylate, etc.; preferably, the crosslinking agent may be selected from N, N-dimethyleneacrylamide and/or methylenebisacrylamide.
According to the composition of the present invention, the ligand may be at least one selected from tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltriethylenetetramine tris (N, N-dimethylaminoethyl) amine, 2' -bipyridine, and the like; preferably, the ligand is selected from pentamethyldiethylenetriamine and/or 2, 2' -bipyridine.
According to the composition of the present invention, the transition metal salt may be selected from at least one of copper salt, iron salt, nickel salt, molybdenum salt and ruthenium salt; preferably, the transition metal salt may be selected from copper salts, such as cuprous bromide (CuBr) and/or cuprous chloride (CuCl).
Further, the invention also provides a preparation method of the aminoglycoside antibiotic imprinted magnetic nanoparticle, which comprises the following steps: the aminoglycoside antibiotic imprinted magnetic nanoparticle is prepared by taking magnetic nanoparticles, template molecules, monosaccharide functional monomers and temperature response type monomers as main raw materials and adopting a surface imprinting method.
According to the technical scheme of the invention, the aminoglycoside antibiotic imprinted magnetic nanoparticle is prepared by adopting a surface imprinting method, such as an activity-controlled free radical polymerization method, preferably a surface transfer atom transfer radical polymerization (SI-ATRP) surface molecular imprinting method.
Preferably, the method for preparing the aminoglycoside antibiotic imprinted magnetic nanoparticle specifically comprises the following steps:
(1) mixing raw material magnetic nanoparticles, template molecules, monosaccharide functional monomers, temperature response type monomers, optional auxiliary monomers, cross-linking agents, ligands and reaction solvents to obtain a mixture, and introducing inert gas into the mixture to remove oxygen;
(2) adding transition metal salt into the mixture under the protection of inert gas, heating under stirring, carrying out free radical polymerization reaction, and carrying out magnetic separation after the reaction is finished to obtain the aminoglycoside antibiotic imprinted magnetic nanoparticles.
According to the preparation method of the invention, the template molecule, the magnetic nano-particle, the monosaccharide functional monomer, the temperature response type monomer, the auxiliary monomer, the cross-linking agent, the ligand and the transition metal salt all have the meanings and the mass ratio as described above.
The addition of the auxiliary monomer can enhance the mechanical strength of the imprinting material and improve the specific recognition capability.
According to the production method of the present invention, the reaction solvent may be water or a mixture of water and an organic solvent. Preferably, the organic solvent may be selected from at least one of toluene, methanol, tetrahydrofuran, and the like. Illustratively, the reaction solvent may be water or a mixture of water and methanol.
According to the preparation method of the invention, the temperature of the free radical polymerization reaction can be 25-80 ℃, such as 40-70 ℃, and exemplarily 60 ℃; the time of the free radical polymerization reaction can be 0.5-48 h, such as 5-36 h and 12-30 h.
According to the preparation method of the invention, the stirring speed can be 200-1500 rpm, such as 500-1200 rpm, 700-1000 rpm.
According to the preparation method of the present invention, the inert gas may be selected from nitrogen and/or argon.
According to the preparation method, the method further comprises the step (3) of cleaning the aminoglycoside antibiotic imprinted magnetic nanoparticles by using an elution solvent, and then drying to obtain a final product.
According to the preparation method of the invention, the elution solvent is a solvent which can dissolve unreacted raw materials, particularly template molecules, but has no influence on the structure of the aminoglycoside antibiotic imprinted magnetic nanoparticle, for example, the elution solvent can be a formic acid aqueous solution (formic acid volume fraction is 0.1-10%, such as 1-8%, 3-6%), a water-acetonitrile mixed solution or a water-acetonitrile-formic acid mixed solution; preferably selecting a water-acetonitrile-formic acid mixed solution with the volume ratio of (70-90): 10-30): 1-5; illustratively, the elution solvent is a water-acetonitrile-formic acid mixed solution with a volume ratio of 80:20: 1.
According to the preparation method of the invention, the drying temperature can be 20-50 ℃, such as 30-50 ℃, and exemplarily, the temperature is 45 ℃; the drying time can be 6-20 h, such as 8-16 h, and exemplarily 12 h.
Furthermore, the invention also provides the aminoglycoside antibiotic imprinted magnetic nanoparticle prepared by the method.
Further, the invention also provides a method for capturing aminoglycoside antibiotics by the aminoglycoside antibiotic imprinted magnetic nanoparticle, which comprises the following steps: and stirring and dispersing the aminoglycoside antibiotic imprinted magnetic nanoparticles in an aqueous phase system containing aminoglycoside antibiotics, heating for adsorption, and performing magnetic separation after the aminoglycoside antibiotic imprinted magnetic nanoparticles capture the aminoglycoside antibiotics.
Preferably, the aqueous system may be selected from the group consisting of ambient water, milk, fruit juice or biochemical systems (e.g. plasma, urine, etc.); preferably, the environmental water is untreated naturally occurring water, such as rain water, river water, or the like.
Preferably, the temperature of the adsorption may be 25 to 90 ℃, such as 30 to 80 ℃, 35 to 60 ℃, and exemplarily, the temperature is 60 ℃; the adsorption time may be 1min to 48h, for example 5min to 24h, 30min to 12h, exemplarily 30 min.
Preferably, the aminoglycoside antibiotic may be present at a concentration of 0.005-0.03. mu.g/mL, such as 0.01-0.0.25. mu.g/mL, illustratively at a concentration of 0.01. mu.g/mL.
Preferably, the mass-to-volume ratio (mg/mL) of the imprinted magnetic nanoparticles to the aqueous system can be (1-5): 1, such as (1-3): 1, and illustratively, the mass-to-volume ratio is 2:1.
Further, the invention also provides a composition, which comprises the aminoglycoside antibiotic imprinted magnetic nanoparticle and an aminoglycoside antibiotic.
Preferably, the aminoglycoside antibiotic is adsorbed on the surface of the aminoglycoside antibiotic imprinted magnetic nanoparticle.
Preferably, the aminoglycoside antibiotic imprinted magnetic nanoparticle and the aminoglycoside antibiotic both have the meaning as described above.
Further, the present invention also provides a method for releasing aminoglycoside antibiotics from the above composition, comprising the steps of: the composition is dispersed in a water phase system, and is stirred for desorption, so that the release of the aminoglycoside antibiotic can be realized.
Preferably, both the composition and the aqueous system have the meaning as described above.
Preferably, the desorption temperature may be 4 to 40 ℃, for example, 5 to 38 ℃, 10 to 37 ℃, and exemplarily, 10 ℃. The desorption time may be 1min to 96h, for example 20min to 60h, 30min to 36h, and exemplarily 30 min.
Furthermore, the invention also provides application of the aminoglycoside antibiotic imprinted magnetic nanoparticle in the field of separation and enrichment, for example, the aminoglycoside antibiotic imprinted magnetic nanoparticle is used as a micro-extraction adsorbent for separation and enrichment of aminoglycoside antibiotics in an aqueous phase system.
Preferably, the aqueous phase system has the meaning as described above.
Further, the invention also provides a kit containing the aminoglycoside antibiotic imprinted magnetic nanoparticle.
The invention has the beneficial effects that:
the imprinting material has excellent adsorption capacity and specificity recognition capacity to aminoglycoside antibiotics, can realize the complete reversible capture and release of the imprinting magnetic nanoparticles to aminoglycoside antibiotics in a water phase only by adjusting the temperature, and has high repeated utilization degree. The method is characterized in the following three aspects:
(1) compared with a control imprinting material synthesized without adding a monosaccharide monomer, the aminoglycoside antibiotic imprinted magnetic nanoparticle has more polar groups capable of interacting with a target analyte-aminoglycoside antibiotic in the structure, for example, a monosaccharide functional monomer forming the imprinting material contains more groups capable of being combined with a target compound through hydrogen bonds and the like, so that the adsorption capacity is more excellent.
(2) Compared with the reported aminoglycoside antibiotic imprinted material, the aminoglycoside antibiotic imprinted magnetic nanoparticle disclosed by the invention can avoid harsh elution conditions (high salt, organic solvent and the like), and reversible capture and release of aminoglycoside antibiotics in a water phase can be realized only by adjusting the temperature.
(3) By testing the process of capturing and releasing the aminoglycoside antibiotic in the aminoglycoside antibiotic imprinted magnetic nanoparticles of the invention for 10 times of circulation at the regulated temperature, the inventors found that the adsorption capacity and selectivity of the aminoglycoside antibiotic imprinted magnetic nanoparticles are not changed obviously, which indicates that the aminoglycoside antibiotic imprinted magnetic nanoparticles have good reusability.
"optionally" in this application means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.
Drawings
FIG. 1 is a Fourier transform infrared spectrum of streptomycin-imprinted magnetic nanoparticles prepared in example 1 of the present invention (A-unmodified bare magnetic nanoparticles, B-streptomycin-imprinted magnetic nanoparticles).
FIG. 2 is a magnetic hysteresis loop diagram of streptomycin imprinted magnetic nanoparticles prepared in example 1 of the present invention (A-unmodified bare magnetic nanoparticles, B-streptomycin imprinted magnetic nanoparticles).
FIG. 3 is a transmission electron microscope image of streptomycin imprinted magnetic nanoparticles prepared in example 1 of the present invention.
FIG. 4 is a graph of adsorption capacities of different imprinted/non-imprinted magnetic nanoparticles to streptomycin;
wherein, MIP 1: streptomycin imprinted magnetic nanoparticles as described in example 1; MIP 2: the conventional imprinted magnetic nanoparticle prepared in comparative example 1; NIP 1: the polymonose-based non-imprinted magnetic nanoparticle prepared in comparative example 2; NIP 2: conventional imprinted magnetic nanoparticles prepared in comparative example 3).
FIG. 5 is a total ion flow diagram of streptomycin capture and release of streptomycin by the streptomycin imprinted magnetic nanoparticles prepared in example 1;
wherein, (a) represents a streptomycin total ion flow diagram in supernatant after being captured in aqueous phase at 60 ℃; (b) represents a flow chart of the total ion flow of streptomycin in the solution after the aqueous phase is released under the condition of 10 ℃.
FIG. 6 is a graph of adsorption capacity of streptomycin-imprinted magnetic nanoparticles prepared in example 1, which were recycled 10 times.
Detailed Description
The blotting material of the present invention, and the preparation method and use thereof, will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
The bromo-functionalized magnetic nanoparticles of example 1 can be prepared by reference to the following references: gai, Q.; qu F.; liu z.; dai r.; zhang y.; superparametric lysozyme surface-imprinted polymer preparation by atom transfer polymerization and its application for protein isolation J.Chromatog.A, 2010,217, 5035-5042.
Example 1 preparation of streptavidin-imprinted magnetic nanoparticles based on polysaccharose by SI-ATRP method and application of imprinted magnetic nanoparticles
(1) Preparation of
200mg of bromine-based surface functionalized magnetic nanoparticles, 20.0mg of methylene bisacrylamide, 200mg of streptomycin sulfate, 100mg of glucose allyl amide, 500 mu L of 2-methyl-2-acrylic acid-2- (2-methoxyethoxy) ethyl ester, 10mg of cuprous bromide and 20mL of water are weighed and placed in a 50mL round-bottom flask, after uniform stirring, argon is introduced for 10 minutes, and then 15 mu L of pentamethyldiethyltriamine is rapidly added in an argon atmosphere. The polymerization mixture was stirred under argon atmosphere for 12h at 60 ℃. After the reaction, 10mL of a mixed solution of water/acetonitrile/formic acid (v/v/v, 80/20/1) was used to wash the product to remove the template molecules and unreacted raw material components, and the solution was separated from the magnetic nanoparticles as solid particles by a magnetic separation method. And finally, placing the synthesized imprinted magnetic nanoparticles in an oven at 45 ℃ for 12 hours to obtain a final product: streptomycin blots magnetic nanoparticles (MIP 1).
FIG. 1 is a Fourier transform infrared spectrum of the streptomycin imprinted magnetic nanoparticles described in this example. As can be seen from FIG. 1, the infrared spectrum B of the imprinted magnetic nanoparticle is 1680cm compared with the unmodified bare magnetic nanoparticle A-1The strong absorption peak appears at 1500cm, which is the stretching vibration characteristic absorption peak of carbonyl (C ═ O) in monomer unit and cross-linking agent unit-1And 1260cm-1The absorption peaks represent the amide II band and the amide III band, respectively, and the results show that the polymer layer is successfully modified on the surface of the bare magnetic nanoparticle.
FIG. 2 is a hysteresis loop of the streptomycin-imprinted magnetic nanoparticle of this example. As can be seen from fig. 2, compared with the unmodified naked magnetic nanoparticles, the prepared streptomycin imprinted magnetic nanoparticles have small magnetic loss, still maintain strong magnetism, and can ensure the realization of rapid magnetic separation.
Fig. 3 is a transmission electron microscope image of the streptomycin imprinted magnetic nanoparticle in the present embodiment, and it can be seen that the particle size of the prepared streptomycin imprinted magnetic nanoparticle is about 10 to 20 nm.
FIG. 5 is a total ion flow diagram of the streptomycin imprinted magnetic nanoparticles capturing and releasing 8 aminoglycoside antibiotics described in this example. As can be seen from fig. 5: reversible capture and release of aminoglycoside antibiotics in the aqueous phase can be achieved by adjusting the temperature.
FIG. 6 is a graph of adsorption capacity of the streptomycin imprinted magnetic nanoparticles of this example after 10 cycles of use (adsorption process such as the adsorption process in (2) application). As can be seen from fig. 6: by adjusting the temperature and circulating for 10 times of capture-release processes, the adsorption capacity and selectivity of the streptomycin imprinted magnetic nanoparticles are not changed obviously, which shows that the streptomycin imprinted magnetic nanoparticles in example 1 have good reusability.
(2) Applications of
The prepared temperature response type imprinted magnetic nano micro-extraction adsorbent is used for enriching aminoglycoside antibiotics in environmental water.
To 1.0mL of ambient water was added a mixture of 8 aminoglycoside antibiotics (streptomycin, neomycin, paromomycin, apramycin, kanamycin, spectinomycin, netilmicin, and tobramycin) at 0.1 μ g/mL, and the above solution was diluted to 10.0mL in a 15.0mL screw white vial, followed by addition of 20.0mg of the synthesized temperature-responsive streptomycin imprinted magnetic nanoparticles. Stirring the mixture at 60 deg.C for 30min, magnetically separating magnetic nanoparticles from the solution after adsorption is completed, and discarding the supernatant. Then, 1mL of ultrapure water was taken as a desorbent and added to the above screw white vial, and stirred at 10 ℃ for 30min, after the target analyte was desorbed from the surface of the magnetic nanoparticles, magnetic separation was performed, and the supernatant was collected and filtered. And analyzing the desorption solution by adopting a high performance liquid chromatography-tandem mass spectrometer. The analysis result of the elution solution shows that the recovery rate of the streptomycin is as high as 97.3 percent.
Comparative example 1
MIP 2-preparation of traditional imprinted magnetic nanoparticles: the same procedure as that for preparing the streptomycin polymyose temperature-responsive imprinted magnetic nanoparticles (MIP1) in example 1 was carried out, and no glucose allylamide was added to the starting materials.
Comparative example 2
NIP 1-preparation of non-imprinted magnetic nanoparticles of polymyxin, which was the same as the preparation of the temperature-responsive imprinted magnetic nanoparticles of streptomycin polymyxa (MIP1) in example 1, no template molecule was added to the raw material.
Comparative example 3
NIP 2-preparation of traditional imprinted magnetic nanoparticles: the same procedure as for the preparation of the conventional imprinted magnetic nanoparticles (MIP2) in comparative example 1 was used, no template molecule was added to the starting material.
FIG. 4 is a graph of adsorption capacities of different imprinted/non-imprinted magnetic nanoparticles to streptomycin (adsorption process as in example 1(2) application). As can be seen from fig. 4, compared with the MIP2 prepared in comparative example 1, the NIP1 prepared in comparative example 2 and the NIP2 prepared in comparative example 3, the imprinted magnetic nanoparticle MIP1 in example 1 has more excellent adsorption capacity (adsorption capacity of about 80 mg/g) because it is a polysaccharidic imprinted material and contains more polar groups capable of interacting with streptomycin.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. An aminoglycoside antibiotic imprinted magnetic nanoparticle, which comprises a magnetic nanoparticle and a monosaccharide temperature-responsive polymer layer located on the outer surface of the magnetic nanoparticle;
the average particle size range of the imprinted magnetic nanoparticles is 10-100 nm;
the monosaccharide temperature-responsive polymer layer is selected from a polymer layer formed by monosaccharide functional monomers and temperature-responsive monomers;
the preparation method of the aminoglycoside antibiotic imprinted magnetic nanoparticle comprises the following steps: preparing the aminoglycoside antibiotic imprinted magnetic nanoparticles from a composition by a surface imprinting method of surface transfer atom transfer radical polymerization (SI-ATRP), wherein the composition comprises magnetic nanoparticles, a cross-linking agent, template molecules, a monosaccharide functional monomer, a temperature-responsive monomer, a transition metal salt and a ligand;
and, the magnetic nanoparticles are selected from magnetic nanoparticles surface-modified with bromo groups;
the cross-linking agent is selected from methylene bisacrylamide;
the template molecule is selected from streptomycin sulfate;
the monosaccharide functional monomer is selected from glucose allyl amide;
the temperature response type monomer is selected from 2-methyl-2-acrylic acid-2- (2-methoxyethoxy) ethyl ester;
the transition metal salt is selected from cuprous bromide;
the ligand is selected from pentamethyldiethylenetriamine;
the mass ratio of the template molecules, the magnetic nanoparticles, the temperature response type monomers and the monosaccharide functional monomers is (20-40): 30-55): 10;
the mass ratio of the magnetic nanoparticles, the cross-linking agent, the ligand and the transition metal salt is (20-40): 2-5): 1.
2. The preparation method of the aminoglycoside antibiotic imprinted magnetic nanoparticle as claimed in claim 1, comprising the step of preparing the aminoglycoside antibiotic imprinted magnetic nanoparticle by a surface imprinting method of surface transfer atom transfer radical polymerization (SI-ATRP) with the composition as a raw material.
3. The method for capturing aminoglycoside antibiotics by using aminoglycoside antibiotics imprinted magnetic nanoparticles as claimed in claim 1, comprising the steps of: and stirring and dispersing the aminoglycoside antibiotic imprinted magnetic nanoparticles in an aqueous phase system containing aminoglycoside antibiotics, heating for adsorption, and performing magnetic separation after the aminoglycoside antibiotics are captured by the imprinted magnetic nanoparticles.
4. A composition comprising aminoglycoside antibiotic imprinted magnetic nanoparticles of claim 1 and an aminoglycoside antibiotic; wherein the aminoglycoside antibiotic is adsorbed on the surface of the aminoglycoside antibiotic imprinted magnetic nanoparticle.
5. Method for releasing aminoglycoside antibiotics from the composition according to claim 4, characterized in that it comprises the following steps: dispersing the composition in an aqueous phase system, and stirring for desorption.
6. The imprinted magnetic nanoparticle of claim 1, as a microextraction adsorbent, for use in separation and enrichment of aminoglycoside antibiotics in aqueous systems.
7. A kit comprising an aminoglycoside antibiotic imprinted magnetic nanoparticle according to claim 1.
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| CN103224589A (en) * | 2013-03-28 | 2013-07-31 | 华东理工大学 | Preparation method and application for aminoglycoside-antibiotic molecularly imprinted polymers |
| CN104356323A (en) * | 2014-10-13 | 2015-02-18 | 北京大学 | Magnetic molecularly imprinted nano-particle as well as preparation method and application thereof |
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| CN103224589A (en) * | 2013-03-28 | 2013-07-31 | 华东理工大学 | Preparation method and application for aminoglycoside-antibiotic molecularly imprinted polymers |
| CN104356323A (en) * | 2014-10-13 | 2015-02-18 | 北京大学 | Magnetic molecularly imprinted nano-particle as well as preparation method and application thereof |
| CN108250360A (en) * | 2017-12-06 | 2018-07-06 | 华南师范大学 | There is aptamers-molecular engram fluorescent optical sensor of dual specificity identification and its preparation method and application to kanamycins |
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