CN112058239A - Cyclodextrin magnetic nano composite material, preparation method and application thereof, and adsorbent - Google Patents
Cyclodextrin magnetic nano composite material, preparation method and application thereof, and adsorbent Download PDFInfo
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Abstract
The invention relates to the technical field of novel functional magnetic nano materials, in particular to a cyclodextrin magnetic nano composite material, a preparation method, application and an adsorbent thereof. The embodiment of the invention provides a cyclodextrin magnetic nano composite material, which comprises cyclodextrin and magnetic nano particles, wherein the cyclodextrin is grafted on the surfaces of the magnetic nano particles through a linking agent, and the linking agent is a compound with a conjugated structure and an electron accepting capacity. The cyclodextrin magnetic nano composite material has excellent adsorption speed and adsorption capacity, and can solve the problems of difficult separation, poor reutilization property and the like of the existing adsorption material.
Description
Technical Field
The invention relates to the technical field of novel functional magnetic nano materials, in particular to a cyclodextrin magnetic nano composite material, a preparation method, application and an adsorbent thereof.
Background
Fluoroquinolone antibiotics are widely used in human beings, livestock and aquatic products as a broad-spectrum bactericide. The product is not enough metabolized in animals and human bodies and released into environmental system after long-term and large-scale use, which affects soil, river and ecological environment. Therefore, research and development of effective fluoroquinolone antibiotic adsorption detection technology and related enrichment materials are receiving much attention.
The cyclodextrin is a commercial natural macrocyclic molecule and comprises a relatively hydrophobic cavity and a hydrophilic outer surface, so that target molecules can be selectively enriched and adsorbed to form a supramolecular complex by using host-guest interaction as a molecular recognition agent; in addition, the cyclodextrin has the advantages of low price, no toxicity, higher practicability, biodegradability and the like, so that the cyclodextrin has important application and research values when being used as an adsorbing material. However, cyclodextrin is easy to lose and separate due to good water solubility, and the practical application of cyclodextrin is limited by poor mechanical properties and recovery capacity, so that the cyclodextrin needs to be modified to effectively exert the advantages of cyclodextrin. Although cyclodextrin is modified in the prior art, the modified material still has the practical application problems of difficult separation, poor reutilization property, poor adsorption effect, high application cost and the like.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a cyclodextrin magnetic nanocomposite material, a preparation method, application and an adsorbent thereof. The embodiment of the invention provides a cyclodextrin magnetic nanocomposite material which has excellent adsorption speed and adsorption capacity and can solve the problems of difficult separation, poor reutilization property and the like of the existing adsorption material.
The invention is realized by the following steps:
in a first aspect, embodiments of the present invention provide a cyclodextrin magnetic nanocomposite material, which includes cyclodextrin and magnetic nanoparticles, where the cyclodextrin is grafted on the surface of the magnetic nanoparticles through a linker, and the linker is a compound having a conjugated structure and an electron donating ability.
In an alternative embodiment, the linking agent is an azobenzene polyacid compound; preferably an azobenzene polycarboxylic acid compound, more preferably azobenzene-4, 4-dicarboxylic acid.
In an alternative embodiment, the magnetic nanoparticles are nanoparticles having a reactive group on the surface that can react with the linker;
preferably, the magnetic nanoparticles are aminated magnetic nanoparticles;
preferably, the magnetic nanoparticles are magnetic nanoparticles with silicon coating layers on the surfaces and are aminated;
preferably, the cyclodextrin magnetic nanocomposite comprises cyclodextrin and magnetic nanoparticles, wherein the magnetic nanoparticles are provided with silicon coating layers on the surfaces and are aminated, and the cyclodextrin is grafted to the surfaces of the magnetic nanoparticles through the azobenzene-4, 4-dicarboxylic acid.
In a second aspect, embodiments of the present disclosure provide a method of preparing a cyclodextrin magnetic nanocomposite material according to any one of the preceding embodiments, comprising: and grafting the cyclodextrin to the surface of the magnetic nanoparticle through a linking agent.
In an alternative embodiment, the step of preparing the magnetic nanoparticles comprises: the method comprises the steps of forming nano particles by using metal salt, coating a silicon coating layer on the surfaces of the nano particles, and then carrying out amination.
In an alternative embodiment, the step of forming nanoparticles comprises: mixing metal salt, weak acid strong base salt and alcohol polymer for reaction;
preferably, the metal salt is an iron salt, preferably ferric chloride;
preferably, the weak acid strong base salt is sodium acetate, and the alcohol polymer is polyethylene glycol;
preferably, the step of forming nanoparticles comprises: ferric chloride, sodium acetate and polyethylene glycol are mixed according to the mass ratio of (1-2.5): (3-4.5): 1, reacting for 6-10 hours at the temperature of 150-;
preferably, the solvent used for the reaction is a polyol solvent, preferably ethylene glycol;
preferably, the amount of ethylene glycol per gram of ferric chloride is 15-25 mL;
preferably, the step of coating the silicon coating layer includes: mixing the nano particles with a silicon source and an alkaline substance for reaction;
preferably, the step of coating the silicon coating layer includes: dispersing the nano particles, mixing the nano particles with the silicon source and the alkaline substance for reaction to form a silicon coating layer and coating the silicon coating layer on the surfaces of the nano particles;
preferably, the silicon source is tetraethoxysilane, the alkaline substance is ammonia water, and the ammonia water with the mass concentration of 15-20% is preferred;
preferably, the step of coating the silicon coating layer includes: dispersing the nano particles in a mixed solution of ethanol and water, and mixing the nano particles with the tetraethoxysilane and the ammonia water for reaction;
preferably, each gram of the nanoparticles corresponds to 100-150 mL of the mixed solution, the volume ratio of ethanol to water in the mixed solution is 3-5:1, 12-18 mL of ammonia water and 3-5 g of tetraethoxysilane are correspondingly added to each gram of the nanoparticles, and the reaction time is 6-10 hours;
preferably, the step of amination comprises: reacting the nanoparticles having the silicon-coated layer coated thereon with an amination reagent to aminate the nanoparticles having the silicon-coated layer coated thereon;
preferably, the step of amination comprises: dispersing the nano particles coated with the silicon coating layer on the surface, and then reacting the nano particles with the amination reagent at the temperature of 100-130 ℃ for 10-12 hours;
preferably, the amination reagent is a compound capable of chemically reacting with the silicon coating layer and also reacting with a linking agent, preferably 3-aminopropyltrimethoxysilane;
preferably, each gram of the nano particles coated with the silicon coating layer corresponds to 10-15 g of 3-aminopropyltrimethoxysilane.
In an alternative embodiment, the preparation method further comprises performing an optimization treatment on the linking agent;
preferably, the optimization process comprises: mixing the linking agent and an acyl chloride reagent to carry out acyl chloride reaction;
preferably, the optimization process comprises: mixing azobenzene-4, 4-dicarboxylic acid and oxalyl chloride under the atmosphere of protective gas to carry out acyl chloride reaction at the temperature of minus 5 to 5 ℃;
preferably, the optimization process comprises: mixing azobenzene-4, 4-dicarboxylic acid and DMF (dimethyl formamide) for ultrasonic treatment, then dropwise adding oxalyl chloride at the temperature of minus 5-5 ℃, and reacting in a protective gas atmosphere;
preferably, the molar ratio of azobenzene-4, 4-dicarboxylic acid to oxalyl chloride is 1: 1-2; the ultrasonic time is 10-20 minutes; 50-100 ml DMF per g azobenzene-4, 4-dicarboxylic acid.
In an alternative embodiment, the step of grafting comprises: dispersing the magnetic nano particles, mixing the magnetic nano particles with an alkaline compound and cyclodextrin, and reacting the mixture with a linking agent;
preferably, the step of grafting comprises: dispersing the magnetic nanoparticles in anhydrous DMF, mixing with triethylamine and cyclodextrin, then dropwise adding a linking agent under the condition of negative 5-5 ℃, and stirring for reaction;
preferably, each gram of the magnetic nanoparticles corresponds to 50-100 ml of anhydrous DMF, and the mass ratio of the magnetic nanoparticles to the triethylamine to the cyclodextrin is 1: (3-5): (5-8); 0.3 to 1 gram linker per gram of the magnetic nanoparticles; the reaction time is 8-12 hours under stirring.
In a third aspect, embodiments of the present disclosure provide an adsorbent comprising the cyclodextrin magnetic nanocomposite material according to any one of the preceding embodiments or the cyclodextrin magnetic nanocomposite material prepared by the method according to any one of the preceding embodiments.
In a fourth aspect, the present invention provides a cyclodextrin magnetic nanocomposite material according to any one of the foregoing embodiments or an application of the cyclodextrin magnetic nanocomposite material prepared by the method according to any one of the foregoing embodiments in antibiotic enrichment or antibiotic content detection;
preferably, the antibiotic is a fluoroquinolone antibiotic.
The invention has the following beneficial effects: according to the embodiment of the invention, the compound with a conjugated structure and an electron supplying capability is selected as the linking agent, so that the specific surface area and the enveloping sites of the cyclodextrin magnetic nanocomposite material are enhanced, and the cyclodextrin magnetic nanocomposite material has the advantages of high adsorption capacity, easiness in separation and good reuse effect. In addition, the cyclodextrin is grafted to the surface of the magnetic nanoparticle by using the linking agent, so that the defects of good water solubility, difficulty in recovery and the like when the cyclodextrin is used as an adsorbing material are effectively overcome, and the preparation and use costs of the material are reduced.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a transmission electron microscope image of nanoparticles prepared in example 1 of the present invention;
FIG. 2 is a transmission electron micrograph of the magnetic nanoparticles prepared in example 1 of the present invention;
FIG. 3 is a transmission electron microscope image of the cyclodextrin magnetic nanocomposite prepared in example 1 of the present invention;
FIG. 4 is a graph showing the Kd values of the adsorption capacities of the magnetic nanoparticles and the cyclodextrin magnetic nanocomposite material prepared in example 1 of the present invention for fluoroquinolone antibiotics;
FIG. 5 is an XPS plot of a cyclodextrin magnetic nanocomposite prepared according to example 1 of the present invention;
FIG. 6 is an infrared spectrum of a material prepared in example 1 of the present invention;
FIG. 7 is a thermogravimetric analysis of the material prepared in example 1 of the present invention;
FIG. 8 is a graph showing the change of the adsorption amount of the cyclodextrin magnetic nanocomposite material with time according to Experimental example 2 of the present invention;
fig. 9 is a graph showing the results of 5 times of recycling of the cyclodextrin magnetic nanocomposite material provided in experimental example 2 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The features and properties of the present invention are described in further detail below with reference to examples.
The embodiment of the invention provides a cyclodextrin magnetic nano composite material, which comprises cyclodextrin and magnetic nano particles, wherein the cyclodextrin is grafted on the surfaces of the magnetic nano particles through a linking agent, and the linking agent is a compound with a conjugated structure and an electron accepting capacity.
The embodiment of the invention introduces the linking agent with electron supply capacity and conjugated structure to enhance the adsorption speed and adsorption capacity of the cyclodextrin magnetic nano composite material, improves the defects of easy water separation and difficult recovery of the cyclodextrin grafted on the surface of the magnetic nano particles, increases the recycling performance of the composite, improves the stability of the cyclodextrin in different environments, and expands the application field of the cyclodextrin. Finally, the practical application problems of difficult separation of the adsorption material, poor reutilization property, poor adsorption effect, high application cost and the like are solved.
Specifically, the linking agent is an azobenzene polybasic acid compound; preferably an azobenzene polycarboxylic acid compound, more preferably azobenzene-4, 4-dicarboxylic acid. The substances can be used as a linking agent to effectively graft the cyclodextrin onto the surface of the magnetic nano-particles, particularly azobenzene-4, 4-dicarboxylic acid can be respectively reacted with the cyclodextrin and the magnetic nano-particles, so that the stability of the formed cyclodextrin magnetic nano-composite material is ensured, the application field of the cyclodextrin magnetic nano-composite material is expanded, meanwhile, the adsorption capacity and the adsorption rate of the cyclodextrin magnetic nano-composite material are improved, and the cyclodextrin magnetic nano-composite material is convenient to recover.
Further, the magnetic nanoparticles are nanoparticles with active groups on the surface which can react with the linking agent; wherein the magnetic nanoparticles are aminated magnetic nanoparticles; the magnetic nanoparticles are aminated magnetic nanoparticles with silicon coating layers arranged on the surfaces. By adopting the magnetic nanoparticles, the interaction between the magnetic nanoparticles and cyclodextrin can be ensured, so that the formed cyclodextrin magnetic nanocomposite material has excellent adsorption performance and separation performance, and the composite material is convenient to recover and reuse.
It should be noted that the metal forming the magnetic nanoparticles provided in the embodiments of the present invention is only iron, but other metals that can form the magnetic nanoparticles or other magnetic nanoparticles that can be acted on by a linker and cyclodextrin in the prior art are also within the scope of the present invention.
And the cyclodextrin employed herein is a commercially available cyclodextrin, such as beta-cyclodextrin.
Specifically, the cyclodextrin magnetic nano composite material comprises cyclodextrin and magnetic nanoparticles, wherein the surfaces of the magnetic nanoparticles are provided with silicon coating layers and are aminated, and the cyclodextrin is grafted to the surfaces of the magnetic nanoparticles through azobenzene-4, 4-dicarboxylic acid.
The embodiment of the invention also provides a preparation method of the cyclodextrin magnetic nanocomposite material, which comprises the following steps:
s1, preparing magnetic nanoparticles;
firstly, mixing metal salt, weak acid strong base salt and alcohol polymer for reaction to form nano particles, wherein the metal salt is iron salt, and ferric chloride is preferred; the weak acid strong base salt is sodium acetate, the alcohol polymer is polyethylene glycol, and the solvent adopted in the reaction is a polyalcohol solvent, preferably ethylene glycol. The adoption of the substances can ensure the formation of the nano particles, ensure that the formed nano particles are dispersed, avoid agglomeration, particularly adopt the polyethylene glycol to fully disperse the formed nano particles, and improve the performance of the formed nano particles.
It should be noted that, the examples of the present invention only list a part of metal salts, weak acid strong base salts, and alcohol polymers, and other metal salts, weak acid strong base salts, and alcohol polymers capable of forming magnetic nanoparticles in the prior art are also within the scope of the present invention.
Further, the step of forming nanoparticles comprises: ferric chloride, sodium acetate and polyethylene glycol are mixed according to the mass ratio of (1-2.5): (3-4.5): 1, reacting for 6-10 hours at the temperature of 150-; the amount of ethylene glycol corresponding to each gram of ferric chloride is 15-25 mL; the proportion is favorable for the formation of nano particles.
Specifically, FeCl is added3Sodium acetate and polyethylene glycol are put into a beaker according to a set proportion, a certain amount of glycol solution is added, and the mixture is stirred evenly on a magnetic stirrer at room temperature (generally 25 ℃). Transferring the uniformly stirred mixed solution into a high-pressure reaction kettle, heating to the reaction temperature for reaction, performing adsorption separation by an external strong magnet after the reaction is finished, and washing by deionized water and ethanol to obtain magnetic nanoparticles.
Then coating a silicon coating layer on the surfaces of the nano particles, specifically, mixing the nano particles with a silicon source and an alkaline substance for reaction; however, the nanoparticles prepared by the above method are easy to agglomerate, and then in order to improve the coating effect, the nanoparticles need to be dispersed before the reaction, specifically, the nanoparticles are dispersed in a mixed solution of ethanol and water, which is beneficial to improving the coating effect.
And after dispersion, adding a silicon source and the alkaline substance while stirring, mixing and reacting, wherein the alkaline substance provides an alkaline environment, which is favorable for hydrolysis of the silicon source and formation of a silicon coating layer. And the silicon source is a silicon coating layer formed by the hydrolysis of molecules through the silicon-oxygen bond action and then coated on the surface of the nanoparticle. The silicon coating layer is arranged, so that the subsequent action of the linking agent and the nano particles can be facilitated, and the cyclodextrin magnetic nano composite material can be formed.
Wherein the silicon source is ethyl orthosilicate, the alkaline substance is ammonia water, and the ammonia water with the mass concentration of 15-20% is preferred; each gram of the nano particles corresponds to 100mL of the mixed solution, the volume ratio of ethanol to water in the mixed solution is 3-5:1, each gram of the nano particles correspondingly adds 12-18 mL of ammonia water and 3-5 g of ethyl orthosilicate, the reaction time is 6-10 h, the reaction temperature is about 40 ℃, and the formation of a silicon coating layer can be further ensured by adopting the conditions and the substances and the silicon coating layer is coated on the surfaces of the nano particles.
Specifically, the prepared nanoparticles are weighed and ultrasonically dispersed in a mixed solution of ethanol and deionized water, then a certain amount of ammonia water and TEOS are added under the stirring condition to react for a period of time, then adsorption separation is carried out through an external strong magnet, and the coated nanoparticles are obtained by washing with deionized water and ethanol.
Then, amination is performed to form magnetic nanoparticles, and specifically, the nanoparticles coated with the silicon coating layer on the surface are reacted with an amination reagent, so that the nanoparticles coated with the silicon coating layer on the surface are aminated. Similarly, in order to improve the amination effect, before amination is performed, the nanoparticles coated with the silicon coating layer need to be dispersed, specifically, the nanoparticles coated with the silicon coating layer are dispersed in ethanol, then oil bath heating is performed to reflux to the reaction temperature, a certain amount of amination reagent is added dropwise, after reaction for a period of time, the amination reagent is adsorbed by an external magnet, and deionized water and ethanol are used for washing to obtain the aminated magnetic nanoparticles.
Wherein the reaction temperature is 100-130 ℃, the reaction time is 10-12 hours, the amination reagent is a compound which can carry out chemical reaction with the silicon coating layer and can also react with the linking agent, and 3-aminopropyl trimethoxy silane is preferable; and each gram of the nano particles coated with the silicon coating layer corresponds to 10-15 g of 3-aminopropyltrimethoxysilane. The adoption of the substances can fully ensure the reaction of the 3-aminopropyltrimethoxysilane and the silicon coating layer, and is also beneficial to the reaction of the aminated magnetic nanoparticles and the linking agent, so that the linking agent can link the magnetic nanoparticles and the cyclodextrin, and the formation of the composite material is ensured.
S2, optimizing;
when the azobenzene polybasic acid compound is used as the linking agent, the azobenzene polybasic acid compound can react with amino groups of the aminated magnetic nanoparticles and can also react with hydroxyl groups of cyclodextrin, but the linking agent has low reaction activity at this time, the cyclodextrin magnetic nanocomposite material is difficult to form, and even if the azobenzene polybasic acid compound reacts, the yield of the formed cyclodextrin magnetic nanocomposite material is low, and the performance of the cyclodextrin magnetic nanocomposite material is not high, so that the linking agent needs to be optimized to improve the reaction activity.
The optimization processing comprises the following steps: and mixing the linking agent with an acyl chloride reagent to perform acyl chloride reaction, wherein the linking agent improves the reactivity in the functionalization process through acyl chloride reaction.
The method comprises the following specific steps: mixing azobenzene-4, 4-dicarboxylic acid and DMF (dimethyl formamide) for ultrasonic treatment, then dropwise adding oxalyl chloride at the temperature of minus 5-5 ℃, and reacting in a protective gas atmosphere; wherein the molar ratio of the azobenzene-4, 4-dicarboxylic acid to the oxalyl chloride is 1: 1-2; the ultrasonic time is 10-20 minutes; 50-100 ml DMF per g azobenzene-4, 4-dicarboxylic acid. The acyl chloride reaction can be ensured to be carried out by adopting the conditions.
More specifically, weighing a certain amount of azobenzene-4, 4-dicarboxylic acid as a linker, dissolving the azobenzene-4, 4-dicarboxylic acid in anhydrous DMF, placing the mixture in an ice bath (generally minus 5 to 5 ℃) after uniform ultrasonic dispersion, dropwise adding a certain amount of oxalyl chloride solution under stirring, stirring the mixture for reaction under the protection of inert gas, and collecting and storing the product in a sealed manner without further purification after the reaction is finished.
Incidentally, the temperature of minus 5 ℃ to 5 ℃ described in the examples of the present invention means that the temperature of the ice bath may be within the above range under the ice bath condition.
It should be noted that although the embodiments of the present invention provide only one acid chloride reagent of oxalyl chloride, other acid chloride reagents that can react with azobenzene-4, 4-dicarboxylic acid or other linking agents are within the scope of the embodiments of the present invention.
S3, grafting;
dispersing the magnetic nanoparticles in anhydrous DMF, mixing with triethylamine and cyclodextrin, then dropwise adding a linking agent under the condition of minus 5-5 ℃, stirring for reaction, then separating the cyclodextrin magnetic nanomaterial by using an external magnetic field, washing and drying to obtain the cyclodextrin magnetic nanocomposite. Wherein each gram of the magnetic nanoparticles corresponds to 50-100 ml of anhydrous DMF, and the mass ratio of the magnetic nanoparticles to the triethylamine to the cyclodextrin is 1: (3-5): (5-8); 0.3 to 1 gram linker per gram of the magnetic nanoparticles; the reaction time is 8-12 hours under stirring. The adoption of the conditions is beneficial to the formation of the composite material and improves the performance of the composite material.
According to the embodiment of the invention, magnetic nanoparticles are used as carriers, modification sites are introduced through the surface coating of the nanoparticles, and a flexible linking agent is introduced through an acyl chlorination reaction so as to bond cyclodextrin functional groups to the surface of a magnetic nanomaterial, thereby obtaining the novel magnetic nano adsorption material. And the preparation method of the process is simple and feasible and the material preparation cost is low.
Further, the embodiment of the present invention also provides an adsorbent, which includes the cyclodextrin magnetic nanocomposite material described in any one of the foregoing embodiments or the cyclodextrin magnetic nanocomposite material prepared by the method described in any one of the foregoing embodiments. The adsorbent has excellent adsorption performance, and is easy to separate and recycle after adsorption.
The embodiment of the invention also provides an application of the cyclodextrin magnetic nanocomposite material according to any one of the preceding embodiments or the cyclodextrin magnetic nanocomposite material prepared by the preparation method according to any one of the preceding embodiments in enrichment of antibiotics or detection of antibiotic content; wherein the antibiotic is a fluoroquinolone antibiotic. The cyclodextrin magnetic nano composite material has high adsorption efficiency and can be applied to adsorption enrichment treatment of fluoroquinolone antibiotics in an environmental sample, so that a simple and easy method and means are provided for environmental pollution treatment and related analyte purification detection.
Example 1
The embodiment provides a preparation method of a cyclodextrin magnetic nanocomposite material, which comprises the following steps:
s1, preparing magnetic nanoparticles;
5g FeCl was weighed310g of sodium acetate and 4g of polyethylene glycol are placed in a beaker, 100mL of ethylene glycol solution is added, and the mixture is stirred uniformly on a magnetic stirrer at room temperature. And then transferring the mixed solution into a high-pressure reaction kettle, heating to 150 ℃ for reaction, after the reaction is finished for 8 hours, naturally cooling to room temperature, performing adsorption separation by using an external strong magnet, and then washing by using deionized water and ethanol to obtain magnetic nanoparticles.
Weighing 1g of the prepared nanoparticles, ultrasonically dispersing the nanoparticles in 120mL of a mixed solution of ethanol and deionized water with a volume ratio of 4:1, adding 12mL of ammonia water with a mass percent of 20% and 4g of TEOS (tetraethylorthosilicate) under stirring, stirring at 40 ℃ for reaction for 6 hours, then carrying out adsorption separation by an external strong magnet, washing with deionized water, and drying with ethanol to obtain the nanoparticles with the silicon coating layer coated on the surface.
Weighing 1g of nanoparticles with silicon coating layers, ultrasonically dispersing the nanoparticles in 100mL of absolute ethyl alcohol, adjusting the temperature of an oil bath to 100 ℃, heating for reflux reaction, dropwise adding 10g of APTMS (3-aminopropyltrimethoxysilane), carrying out reflux reaction for 10 hours, naturally cooling to room temperature, adsorbing by an external magnet, washing with deionized water and ethanol, and drying to obtain the aminated magnetic nanoparticles.
S2, optimizing;
weighing 0.5g of linking agent azobenzene-4, 4-dicarboxylic acid, dissolving in 50mL of anhydrous DMF, ultrasonically dispersing for 10 minutes, placing in an ice bath after uniform dispersion, dropwise adding 0.35g of oxalyl chloride solution under stirring, stirring under the protection of inert gas nitrogen for reaction, and collecting the product for sealed storage without further purification after the reaction is finished.
S3, grafting;
1g of the magnetic nanoparticles are weighed and ultrasonically dispersed in 60mL of anhydrous DMF, then 3g of TEA (triethylamine) and 5g of beta-cyclodextrin are sequentially added, and the mixture is fully stirred to form a uniform mixed solution. And then placing the mixture into an ice bath, dropwise adding 30mL of the linker (namely 0.3 g of the linker) after acyl chlorination, reacting for 8 hours under a stirring condition, separating the cyclodextrin magnetic nano-material by using an external magnetic field after the reaction is finished, washing, and drying in vacuum to obtain the cyclodextrin magnetic nano-composite material.
Example 2
The embodiment provides a preparation method of a cyclodextrin magnetic nanocomposite material, which comprises the following steps:
s1, preparing magnetic nanoparticles;
6g FeCl was weighed314g of sodium acetate and 4g of polyethylene glycol are placed in a beaker, 150mL of ethylene glycol solution are added, and the mixture is stirred uniformly on a magnetic stirrer at room temperature. And then transferring the mixed solution into a high-pressure reaction kettle, heating to 180 ℃ for reaction, after the reaction is finished for 10 hours, naturally cooling to room temperature, performing adsorption separation by using an external strong magnet, and then washing by using deionized water and ethanol to obtain the nano particles.
Weighing 1.5g of the prepared nanoparticles, ultrasonically dispersing the nanoparticles in 160mL of mixed solution of ethanol and deionized water with the volume ratio of 5:1, adding 20mL of ammonia water with the mass percent of 15% and 5g of TEOS under the stirring condition, stirring for reacting for 8 hours, then performing adsorption separation by an external strong magnet, washing with deionized water and ethanol, and drying to obtain the nanoparticles with the silicon coating layer coated on the surface.
Weighing 1.5g of the nanoparticles coated with the silicon coating layer on the surface, ultrasonically dispersing the nanoparticles in 150mL of absolute ethyl alcohol, adjusting the temperature of an oil bath to 120 ℃, heating for reflux reaction, dropwise adding 15g of APTMS, carrying out reflux reaction for 12h, naturally cooling to room temperature, adsorbing by an external magnet, washing with deionized water and ethanol, and drying to obtain the aminated magnetic nanoparticles.
S2, optimizing;
weighing 1g of linking agent azobenzene-4, 4-dicarboxylic acid, dissolving in 100mL of anhydrous DMF, placing in an ice bath after ultrasonic dispersion is uniform, dropwise adding 0.5g of oxalyl chloride solution under stirring, stirring and reacting under the protection of inert gas nitrogen, and collecting the product for sealed storage without further purification after the reaction is finished.
S3, grafting;
2g of the magnetic nanoparticles formed by amination above were weighed and ultrasonically dispersed in 150mL of anhydrous DMF, followed by addition of 8g of TEA and 12g of cyclodextrin in that order and sufficient stirring to obtain a homogeneous mixed solution. And then placing the mixture into an ice bath, dropwise adding 70mL of the linker after acyl chlorination (namely 0.35g of linker per gram of magnetic nanoparticles), reacting for 12 hours under a stirring condition, separating the cyclodextrin magnetic nanomaterial by using an external magnetic field after the reaction is finished, washing, and drying in vacuum to obtain the cyclodextrin magnetic nanocomposite.
Example 3 to example 4
Examples 3-4 all provide a method of preparing cyclodextrin magnetic nanocomposites that is essentially the same as the method of preparing cyclodextrin magnetic nanocomposites provided in example 1, except that the conditions specifically employed are different. Specifically, the method comprises the following steps:
example 3:
s1, preparing magnetic nanoparticles: the mass ratio of ferric chloride to sodium acetate to polyethylene glycol is 1:3:1, the amount of ethylene glycol corresponding to each gram of ferric chloride is 15mL, the reaction temperature is 200 ℃, and the reaction time is 6 h. The mass concentration of ammonia water is 20%, each gram of the nano particles corresponds to 100 milliliters of mixed solution of ethanol and water with the volume ratio of 3:1, each gram of the nano particles corresponds to 18 milliliters of the ammonia water and 3 grams of tetraethoxysilane, and the reaction time of coating is 10 hours. The reaction temperature of amination is 130 ℃, the reaction time is 10 hours, and each gram of the nano particles coated with the silicon coating layer corresponds to 12g of 3-aminopropyltrimethoxysilane.
S2, optimization: the molar ratio of azobenzene-4, 4-dicarboxylic acid to oxalyl chloride is 1: 1; the ultrasonic time is 10 minutes; 150ml DMF per g of azobenzene-4, 4-dicarboxylic acid.
S3, grafting: each gram of the magnetic nano-particles corresponds to 50 milliliters of anhydrous DMF, and the mass ratio of the magnetic nano-particles to the triethylamine to the cyclodextrin is 1:5: 8; 0.3 grams linker per gram of magnetic nanoparticle; the reaction time was stirred for 10 hours.
Example 4
S1, preparing magnetic nanoparticles: the mass ratio of ferric chloride to sodium acetate to polyethylene glycol is 2.5:4.5:1, the amount of ethylene glycol per gram of ferric chloride is 15mL, the reaction temperature is 200 ℃, and the reaction time is 6 h. The mass concentration of ammonia water is 18%, each gram of the nano particles corresponds to 150 milliliters of mixed solution of ethanol and water with the volume ratio of 3:1, each gram of the nano particles corresponds to 18 milliliters of the ammonia water and 3 grams of tetraethoxysilane, and the reaction time of coating is 10 hours. The reaction temperature of amination is 130 ℃, the reaction time is 12 hours, and each gram of the nano particles coated with the silicon coating layer corresponds to 12g of 3-aminopropyltrimethoxysilane.
S2, optimization: the molar ratio of azobenzene-4, 4-dicarboxylic acid to oxalyl chloride is 1: 2; the ultrasonic time is 20 minutes; 150ml DMF per g of azobenzene-4, 4-dicarboxylic acid.
S3, grafting: each gram of the magnetic nano-particles corresponds to 100 milliliters of anhydrous DMF, and the mass ratio of the magnetic nano-particles to the triethylamine to the cyclodextrin is 1:5: 8; 1 gram linker per gram of magnetic nanoparticle; the reaction time was stirred for 10 hours.
Characterization of
(1) Respectively performing transmission electron microscope scanning on the nanoparticles, the magnetic nanoparticles and the cyclodextrin magnetic nanocomposite material prepared in example 1, and detecting results with reference to fig. 1-3, wherein fig. 1 is a transmission electron microscope image of the nanoparticles prepared in example of the present invention, and fig. 2 is a transmission electron microscope image of the magnetic nanoparticles prepared in example 1 of the present invention; FIG. 3 shows the cyclodextrin magnetic nanocomposite prepared in example 1 of the present invention.
The particle size of the nano particles prepared by the method is about 300nm, the nano particles have uniform spherical structures, and the nano particles have better dispersibility. Meanwhile, an obvious gray-black double-layer structure can be seen after coating treatment in fig. 2, which shows that a silicon coating layer with uniform thickness is formed on the surface of the magnetic nano-particle, so that the magnetic core structure can be effectively protected, and subsequent further modification can be performed. After grafting treatment, the grey-white-grey-black three-layer sandwich structure (fig. 3) corresponds to the cyclodextrin shell layer, the silicon dioxide layer and the nano magnetic core respectively. Meanwhile, the core-shell sandwich structure is also beneficial to the adsorption of target analytes, so that the material has higher adsorption efficiency. Therefore, the cyclodextrin functionalized magnetic nanocomposite material, namely the cyclodextrin magnetic nanocomposite material, can be effectively prepared by the method.
(2) Cyclodextrin magnetic nanocomposite (Fe) prepared in example 13O4@SiO2@ CD) were subjected to X-ray photoelectron spectroscopy (XPS) characterization to demonstrate the chemical composition of the material and the chemical state of the relevant elements, with the results shown in fig. 5.
The element absorption peaks in the element full-scan spectrum of a in FIG. 5 correspond to five elements of Fe 2p, O (1s,2s), N1 s, C1s and Si (2s,2p), respectively (a in FIG. 5). Among them, the C1s high resolution spectra have binding energies of 284.8eV,285.8eV,286.7eV and 288.6eV respectively corresponding to the C-C/C-H, C-N/C-O, C ═ O and O-C ═ O/N-C ═ O bonds of the nanomaterials, indicating that the cyclodextrin was successfully grafted on the surface of the magnetic nanoparticles (b in fig. 5). Meanwhile, Si-O, C ═ O and O-C ═ O in the high-resolution spectrum of O1s further indicate the functionalization effect of the material (C in FIG. 5). In addition, the binding energies of 399.8eV and 400.1eV in the N1 s high resolution spectrum correspond to C-N and N ═ N bonds in the linker azobenzene-4, 4-dicarboxylic acid, respectively, indicating that the nanocomposite obtains the functionalization effect by reacting the nanoparticles with the cyclodextrin functional groups through the linker (d in fig. 5).
(3) For the nanoparticles provided in example 1, i.e., iron oxide (Fe)3O4) Silicon-coated nanoparticles (Fe)3O4@SiO2) Aminated magnetic nanoparticles (Fe)3O4@SiO2@NH2) And cyclodextrin magnetic nanocomposite (Fe)3O4@SiO2@ CD) was subjected to infrared spectroscopy, and the results are shown in fig. 6.
At 578cm-1The strong absorption corresponds to the Fe-O stretching vibration absorption peak of the magnetic nano-particles. 1087cm-1The strong absorption is Si-O-Si stretching vibration absorption peak, which shows that a silicon dioxide coating layer is formed on the surface of the material, and the thickness is 1780cm-1And 1721cm-1The absorption peak of the linking agent corresponds to C ═ O stretching vibration, 3436cm-1And 2930cm-1Absorption peaks respectively correspond to the asymmetric stretching vibration absorption peaks of O-H and C-H groups, which shows that the cyclodextrin functional groups are successfully connectedIs branched on the surface of the nanometer material.
(4) For the nanoparticles provided in example 1, i.e., iron oxide (Fe)3O4) Silicon-coated nanoparticles (Fe)3O4@SiO2) Aminated magnetic nanoparticles (Fe)3O4@SiO2@NH2) And cyclodextrin magnetic nanocomposite (Fe)3O4@SiO2@ CD) at 25-750 deg.C for 10min-1Thermogravimetric analysis of the temperature rise rate of (2) was carried out, and the result is shown in FIG. 7.
The nano material has slight weight loss when the initial temperature is less than 200 ℃, because a small amount of water vapor adsorbed on the surface of the material is evaporated, and the nano material prepared by the method is not easy to decompose and has better thermal stability. The magnetic nanocomposite material undergoes thermal decomposition starting from 230 ℃ with an increase in temperature, and the weight loss remains substantially stable after reaching 430 ℃. The weight loss is mainly attributed to the pyrolysis of the surface linking agent of the nanometer material and the functional group of the cyclodextrin. The thermogravimetric result also shows that the surface of the nano material is successfully subjected to functionalized grafting.
Experimental example 1
The Kd values of the fluoroquinolone antibiotics adsorbed by the magnetic nanoparticles and the cyclodextrin magnetic nanocomposite prepared in the embodiment 1 of the invention are respectively detected.
Respectively carrying out adsorption experiments of the target fluoroquinolone antibiotics on the prepared magnetic nano material and the cyclodextrin functionalized nano composite material under the optimal experimental conditions, then detecting by using HPLC-MS/MS, and evaluating the adsorption performance of the material by a distribution coefficient Kd value. Wherein the Kd value is calculated by equation (1).
Kd＝(Ci-Ce)/Ce×V/m (1)
Wherein, CiAnd CeRespectively represents the concentration of the fluoroquinolone antibiotic in the solution before and after adsorption equilibrium; v and m represent the volume of the solution and the amount of the added adsorbent in the adsorption experiment, respectively.
A higher Kd value indicates a stronger adsorption capacity of the material for the target analyte. The results of fig. 4 show that the adsorption capacity of the functionalized nanocomposite material to the target fluoroquinolone antibiotic is obviously stronger than that of the non-functionalized material. Presumably, due to the polyhydroxy and pore size structure of the cyclodextrin functional groups, hydrogen bonds and host-guest inclusion complex structures are formed between the material and the target analyte. Meanwhile, the benzene ring and the N heterocyclic ring structure in the linking agent are also beneficial to the formation of pi-pi interaction and electron co-action between the material and an analyte, so that the adsorption performance of the material is further enhanced.
Experimental example 2
Separately weighing Fe3O4@SiO2And Fe after functionalization3O4@SiO2The @ CD nanocomposite material is 10mg, the adsorption experiment is carried out on the fluoroquinolone antibiotic with the concentration of 10mg/L within 2-120min at different time, HPLC-MS/MS detection is carried out, and the adsorption kinetics of the material are simulated. Wherein the change of the adsorption capacity of the material with time is described by the formula (2).
Qt＝(Ci-Ct)×V/m (2)
Wherein, CiAnd CtRepresents the initial and post-adsorption equilibrium concentrations of the antibiotic in the solution for time t; v and m represent the volume of the solution and the amount of the adsorbent, respectively.
As shown in fig. 8, the adsorption performance of the material increased with time and reached equilibrium in a shorter time (10min), indicating that the nanomaterial has a faster adsorption rate for the target analyte. Simultaneously, Fe after functionalization3O4@SiO2The adsorption capacity of the @ CD nanocomposite material is higher than that of Fe3O4@SiO2Further illustrates that the inclusion compound structure formed between the cyclodextrin functional group and the linker and the target antibiotic and the pi-pi interaction have great influence on the improvement of the adsorption performance of the material. In addition, the adsorption of the material is respectively simulated by the quasi-first-order dynamics, the quasi-second-order dynamics and the Elovich dynamics, and the result shows that the adsorption of the material is more suitable for the quasi-second-order dynamics, which shows that the adsorption rate control factor between the nano material and the antibiotic is mainly due to the influence of the chemical process, and further shows that the adsorption of the nano material to the antibiotic is also carried outMainly through the chemical bond forces between the functional groups and the linker and the target analyte.
The experiment also investigated the reusability of the nanomaterial, and the result of five adsorption-desorption experiments on the nanomaterial is shown in fig. 9. The experimental result shows that Fe3O4@SiO2The adsorption effect of the @ CD nanocomposite on the target object can be basically kept stable during the first three times of recycling. With the increase of the repeated times, the adsorption performance of the material is reduced, and probably because the functional groups on the surface of the nano material are lost due to repeated utilization and regeneration. But the adsorption efficiency after five times of reutilization can still reach more than 80 percent, and further shows that the material prepared by the method has better reutilization property.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. 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 (10)
1. The cyclodextrin magnetic nano composite material is characterized by comprising cyclodextrin and magnetic nano particles, wherein the cyclodextrin is grafted to the surfaces of the magnetic nano particles through a linking agent, and the linking agent is a compound with a conjugated structure and an electron accepting capacity.
2. The cyclodextrin magnetic nanocomposite of claim 1, wherein the linker is an azobenzene polyacid compound; preferably an azobenzene polycarboxylic acid compound, more preferably azobenzene-4, 4-dicarboxylic acid.
3. The cyclodextrin magnetic nanocomposite of claim 2, wherein the magnetic nanoparticles are nanoparticles having a surface with a reactive group that can react with the linker;
preferably, the magnetic nanoparticles are aminated magnetic nanoparticles;
preferably, the magnetic nanoparticles are aminated magnetic nanoparticles with a silicon coating layer arranged on the surface;
preferably, the cyclodextrin magnetic nanocomposite comprises cyclodextrin and magnetic nanoparticles, wherein the magnetic nanoparticles are provided with silicon coating layers on the surfaces and are aminated, and the cyclodextrin is grafted to the surfaces of the magnetic nanoparticles through the azobenzene-4, 4-dicarboxylic acid.
4. A method of preparing a cyclodextrin magnetic nanocomposite material of any one of claims 1-3, comprising: and grafting the cyclodextrin to the surface of the magnetic nanoparticle through a linking agent.
5. The method of claim 4, wherein the step of preparing the magnetic nanoparticles comprises: the method comprises the steps of forming nano particles by using metal salt, coating a silicon coating layer on the surfaces of the nano particles, and then carrying out amination.
6. The method of claim 5, wherein the step of forming nanoparticles comprises: mixing metal salt, weak acid strong base salt and alcohol polymer for reaction;
preferably, the metal salt is an iron salt, preferably ferric chloride;
preferably, the weak acid strong base salt is sodium acetate, and the alcohol polymer is polyethylene glycol;
preferably, the step of forming nanoparticles comprises: ferric chloride, sodium acetate and polyethylene glycol are mixed according to the mass ratio of (1-2.5): (3-4.5): 1, reacting for 6-10 hours at the temperature of 150-;
preferably, the solvent used for the reaction is a polyol solvent, preferably ethylene glycol;
preferably, the amount of ethylene glycol per gram of ferric chloride is 15-25 mL;
preferably, the step of coating the silicon coating layer includes: mixing the nano particles with a silicon source and an alkaline substance for reaction;
preferably, the step of coating the silicon coating layer includes: dispersing the nano particles, mixing the nano particles with the silicon source and the alkaline substance for reaction to form a silicon coating layer and coating the silicon coating layer on the surfaces of the nano particles;
preferably, the silicon source is tetraethoxysilane, the alkaline substance is ammonia water, and the ammonia water with the mass concentration of 15-20% is preferred;
preferably, the step of coating the silicon coating layer includes: dispersing the nano particles in a mixed solution of ethanol and water, and mixing the nano particles with the tetraethoxysilane and the ammonia water for reaction;
preferably, each gram of the nanoparticles corresponds to 100-150 mL of the mixed solution, the volume ratio of ethanol to water in the mixed solution is 3-5:1, 12-18 mL of ammonia water and 3-5 g of tetraethoxysilane are correspondingly added to each gram of the nanoparticles, and the reaction time is 6-10 hours;
preferably, the step of amination comprises: reacting the nanoparticles having the silicon-coated layer coated thereon with an amination reagent to aminate the nanoparticles having the silicon-coated layer coated thereon;
preferably, the step of amination comprises: dispersing the nano particles coated with the silicon coating layer on the surface, and then reacting the nano particles with the amination reagent at the temperature of 100-130 ℃ for 10-12 hours;
preferably, the amination reagent is a compound capable of chemically reacting with the silicon coating layer and also reacting with a linking agent, preferably 3-aminopropyltrimethoxysilane;
preferably, each gram of the nano particles coated with the silicon coating layer corresponds to 10-15 g of 3-aminopropyltrimethoxysilane.
7. The method of claim 4, further comprising optimizing the linker;
preferably, the optimization process comprises: mixing the linking agent and an acyl chloride reagent to carry out acyl chloride reaction;
preferably, the optimization process comprises: mixing azobenzene-4, 4-dicarboxylic acid and oxalyl chloride under the atmosphere of protective gas to carry out acyl chloride reaction at the temperature of minus 5 to 5 ℃;
preferably, the optimization process comprises: mixing azobenzene-4, 4-dicarboxylic acid and DMF (dimethyl formamide) for ultrasonic treatment, then dropwise adding oxalyl chloride at the temperature of minus 5-5 ℃, and reacting in a protective gas atmosphere;
preferably, the molar ratio of azobenzene-4, 4-dicarboxylic acid to oxalyl chloride is 1: 1-2; the ultrasonic time is 10-20 minutes; 50-100 ml DMF per g azobenzene-4, 4-dicarboxylic acid.
8. The method of any one of claims 4-7, wherein the step of grafting comprises: dispersing the magnetic nano particles, mixing the magnetic nano particles with an alkaline compound and cyclodextrin, and reacting the mixture with a linking agent;
preferably, the step of grafting comprises: dispersing the magnetic nanoparticles in anhydrous DMF, mixing with triethylamine and cyclodextrin, then dropwise adding a linking agent under the condition of negative 5-5 ℃, and stirring for reaction;
preferably, each gram of the magnetic nanoparticles corresponds to 50-100 ml of anhydrous DMF, and the mass ratio of the magnetic nanoparticles to the triethylamine to the cyclodextrin is 1: (3-5): (5-8); 0.3 to 1 gram linker per gram of the magnetic nanoparticles; the reaction time is 8-12 hours under stirring.
9. An adsorbent comprising the cyclodextrin magnetic nanocomposite according to any one of claims 1 to 3 or the cyclodextrin magnetic nanocomposite prepared by the method of preparing the cyclodextrin magnetic nanocomposite according to any one of claims 4 to 8.
10. Use of a cyclodextrin magnetic nanocomposite material according to any one of claims 1 to 3 or a cyclodextrin magnetic nanocomposite material prepared by the method of any one of claims 4 to 8 for enriching an antibiotic or for detecting the content of an antibiotic;
preferably, the antibiotic is a fluoroquinolone antibiotic.
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