CN105032380B - Preparation and application of endohedral triolein multi-vesicle magnetic nanoparticles - Google Patents

Abstract

The invention belongs to the technical field of environmental pollution detection, and relates to the preparation and application of triolein-embedded multivesicle magnetic nanoparticles. Based on magnetic nanomaterials, the surface coating of the magnetic nanoparticle has similar adsorption kinetics to water hydrophobic pollutants of organisms. The characteristic triolein cellulose acetate composite membrane particles have a core-shell structure with embedded multivesicles. The cellulose acetate membrane has a well-developed void structure, which improves the exchange rate of pollutants inside and outside the membrane, and shortens the experimental period of the biological toxicity test. , to avoid the interference of biological culture conditions, used to simulate, detect and analyze the concentration distribution of environmental pollutants, and test the adsorption kinetics and biological effectiveness of animal cells to hydrophobic pollutants; the design principle is reliable, the preparation process steps are simple, and the design The route is mature, environmentally friendly, with large specific surface area, well-developed surface voids, and good compatibility with water bodies, which is conducive to the diffusion of pollutants in water bodies, and can shorten the sampling time according to differences in environmental conditions.

Description

Preparation and application of triolein-embedded multivesicular magnetic nanoparticles

Technical field:

The invention belongs to the technical field of environmental pollution detection, and relates to a process technology for preparing micro-nano particles with the function of simulating the adsorption of organic pollutants by biological cells, which is used for simulating, detecting and studying the concentration distribution of environmental pollutants, and testing the hydrophobicity of animal cells. Adsorption kinetics and bioavailability of sexual pollutants, especially the preparation and application of triolein-embedded multivesicular magnetic nanoparticles.

Background technique:

At present, due to insufficient anticipation of the negative impact of highly developed industries, it has led to a global environmental pollution crisis, in which water pollution is particularly serious. The risk of pollutants to the ecological environment is mainly manifested in the interference or toxicity of organisms and biological communities. When the concentration of pollutants in the organism exceeds the tolerance limit of the organism, it will have a toxic effect on the tissues and organs of the organism, hinder the normal metabolism of the organism, and lead to biological disease or death; the development of the chemical industry has led to the types and types of pollutants in the environment. The number of these compounds has increased significantly. The harm of these compounds to the ecological environment and the human body requires a large number of toxicology experiments to test their biological toxicity and environmental risk. For the diversity of the environment, the exposure level of pollutants in the environment and the biological effectiveness Toxicity experiments need to be carried out to verify the relationship between pollutants. In the pollutant toxicity test, the conventional experimental species mainly include fish, amphibians, microorganisms, benthic organisms and microorganisms, etc. In the toxicity test, the tested In the process of biological domestication, toxicity exposure and detection, it usually occupies a large area of test sites, consumes a lot of time, manpower, material resources and financial resources. At the same time, the process of collecting and storing biological samples in the field is strict, which easily affects experimental errors and brings great harm to toxicity test research. Great inconvenience; polycyclic aromatic hydrocarbons (PAHs) widely and persistently exist in the water environment, and have attracted much attention because of their carcinogenicity, teratogenicity and enrichment to organisms; PAHs are mainly transmitted through oil refining spills, transportation, The incomplete combustion of fossil fuels and organic matter, coke oven process and discharge into the environment, PAHs in water mainly come from the process of atmospheric deposition; the adsorption of PAHs by aquatic organisms is mainly obtained through physiological active transport and passive diffusion, three Olein is widely distributed in animal and plant cells, and its strong hydrophobicity increases the adsorption and enrichment of hydrophobic pollutants by organisms. The solubility in water is usually at the level of pg/L～ng/L. Traditional analysis methods cannot be accurate and fast , Simultaneous detection of trace PAHs in water bodies; in recent years, China's PAHs emissions have increased significantly with industrial development and population growth, and it is necessary to quickly and accurately detect PAHs and other persistent organic pollutants in environmental media. The study of the diffusion behavior of pollutants in biological cells is of great significance for exploring the toxicity characteristics and environmental behavior of pollutants. Therefore, efficient and fast pollutant pre-treatment technologies are in urgent need of research and development; therefore, the development of fast and stable detection and evaluation of water bodies The research on the concentration range of pollutants in living organisms and the exploration of new materials to control environmental pollution are new technologies that urgently need to solve the environmental risks of pollutants.

Invention content:

The purpose of the present invention is to overcome the shortcomings of the prior art, and seek to prepare a kind of embedded triolein multivesicle magnetic nanoparticle with the characteristics of simulating biological cells and adsorption kinetics of organic pollutants, based on magnetic nanomaterials , by coating triolein and cellulose, a core-shell structure with embedded multivesicles is obtained, which has good adsorption performance for hydrophobic pollutants, and the pore structure of cellulose acetate membrane is developed, which improves the adsorption of pollutants inside and outside the membrane. The exchange speed shortens the experiment period of the biological toxicity test and avoids the interference of biological culture conditions.

In order to achieve the above-mentioned purpose, the preparation process of the embedded triolein multivesicular magnetic nanoparticles involved in the present invention, with the help of the rapid separation performance of the magnetic nanomaterials under an external magnetic field, has a surface coating similar to biological hydrophobic pollution to water bodies Triolein cellulose acetate composite membrane particles with adsorption kinetics characteristics, the specific preparation steps are:

(1) Co-precipitation method to synthesize Fe ₃ O ₄ MNPs aqueous solution: 2.0g FeCl ₂ 4H ₂ O and 5.2g FeCl ₃ 6H ₂ O were dissolved in 25ml of oxygen-free deionized water, and 0.85mL of concentrated hydrochloric acid was added to form a mixed solution , under nitrogen protection and constant stirring, the mixed solution was added dropwise to 250mL 1.5M NaOH solution to obtain Fe ₃ O ₄ MNPs, and Fe ₃ O ₄ MNPs were washed with 200mL deionized water for 5-10 times, and then suspended and stored in In 220mL of deionized water, an aqueous solution of Fe ₃ O ₄ MNPs with a concentration of 10mg/mL and a particle size of 10nm was prepared;

(2) Preparation of emulsion: add cellulose acetate with a concentration of 0.02g/mL and triolein with a concentration of 0.2g/mL into 25mL of acetone to form a mixture, place the sealed mixture on a shaker at 100r /min shake for 1-9 hours, make it fully mixed, and complete the preparation of the emulsion;

(3) Preparation of Fe ₃ O ₄ @CTAB MNPs: Take 10 mL of the Fe ₃ O ₄ MNPs solution synthesized in step (1) and add it to 10 mL of cetyltrimethylammonium bromide (CTAB) aqueous solution with a concentration of 5 mg/mL A mixed solution was formed in the mixture, and the mixed solution was sonicated for 10-15min at room temperature, so that the surface of Fe ₃ O ₄ MNPs was fully modified by CTAB, and Fe ₃ O ₄ @CTABMNPs with a radial structure on the hydrophobic surface were obtained, which were electrostatically adsorbed by CTAB cationic terminals On the surface of Fe3O4@CTAB MNPs magnetic nanomaterials;

(4) Preparation of emulsified Fe ₃ O ₄ @CTAB MNPs: Heat the water bath to 35±2°C, and mechanically stir at 300r/min, add the Fe ₃ O ₄ @CTAB MNPs prepared in step (3) dropwise A mixed solution is formed in the emulsion prepared in step (2), and 50 ml of NaOH aqueous solution with a pH value of 10.0 is added dropwise to the mixed solution to obtain emulsified Fe ₃ O ₄ @CTAB MNPs;

(5) Preparation of triolein-embedded multivesicular magnetic nanoparticles: Concentrate the emulsified Fe ₃ O ₄ @CTABMNPs prepared in step (4) to a viscous state with a rotary evaporator at a temperature of 28-32°C and freeze-dry , Fe ₃ O ₄ @Triolein@CAMMNPs were obtained, and Fe ₃ O ₄ @Triolein@CAM MNPs were soaked in deionized water at 10°C for 12 hours to obtain triolein-embedded multivesicular magnetic nanoparticles.

The present invention relates to the specific process of the embedded triolein multivesicle magnetic nanoparticles when applied to simulate, detect and analyze the concentration distribution of environmental pollutants, and test the adsorption kinetics and biological effectiveness of animal cells to hydrophobic pollutants The steps are:

(1), first place 1 to 2 parts by weight of triolein-embedded multivesicular magnetic nanoparticles in the water to be tested, stir for 5 to 10 minutes, and mix them uniformly to form a mixed solution;

(2), then the mixed solution was left to stand for 3 hours and the nanoparticles were separated with a magnet, and the supernatant was poured out;

(3) According to the volume ratio of 1:3, take 20mL of acetonitrile and 60mL of n-hexane and stir to form a mixed solution. The mixed solution is ultrasonically cleaned for 10min with 5mL each time to elute the organic pollutants enriched on the nanoparticles, and 20mL containing the target compound eluent;

(4) Concentrate the eluate obtained in step (3) with a nitrogen blower, and set the volume to 1ml, then filter it into a 1.5mL liquid phase bottle with a 0.22 μm glass fiber filter membrane, and use GC/UPLC- MS detects PAHs (polycyclic aromatic hydrocarbons); add triolein-embedded multivesicular magnetic nanoparticles to 1 L of water containing 100 ng/L acrylic pyrene, and enrich for 48 hours under slow stirring, at 0.25, Samples were taken at 0.5, 1, 2, 4, 8, 16, 24, 36, and 48, respectively, and the amount of enriched PAHs was detected. After kinetic experiment analysis, it was shown that the embedded triolein multivesicular magnetic nanoparticles had a positive effect on the water body. The adsorption kinetics of PAHs gradually reaches saturation with the increase of time, which has the kinetic characteristics of the adsorption of pollutants by aquatic organisms.

Compared with the prior art, the present invention takes Fe ₃ O ₄ MNPs as the core, modifies the surface of the multi-vesicle rupture structure containing triolein, and then directly adds it to natural water bodies to detect polycyclic aromatic diameters in water bodies. The concentration of pollution simulates the adsorption kinetics of water biological cells to polycyclic aromatic diameter pollution and other hydrophobic organic substances; its design principle is reliable, the preparation process steps are simple, the design route is mature, environmental protection and pollution-free, large specific surface area, and surface voids Developed, has good compatibility with water bodies, is conducive to the diffusion of pollutants in water bodies, and can shorten the sampling time according to differences in environmental conditions.

Description of drawings:

Figure 1 is a schematic diagram of the preparation principle of the present invention.

Fig. 2 is a scanning electron microscope spectrogram of Fe ₃ O ₄ MNPs involved in the present invention.

Fig. 3I is an infrared spectrum characterization diagram of CTAB modified on Fe ₃ O ₄ MNPs involved in the present invention.

Fig. 3II is an infrared spectrum characterization diagram of the cellulose acetate membrane successfully modified on Fe ₃ O ₄ @CTAB MNPs involved in the present invention.

Fig. 3III shows that the infrared absorption peak gradually increases with the addition of cellulose acetate and triolein in the conditions of a, 2.5a, 7.5a and 15a respectively according to the present invention.

Fig. 3Ⅳ is the infrared spectrum of the reduction of the efficiency of cellulose acetate coated on Fe ₃ O ₄ @CTAB MNPs with the increase of cellulose acetate and triolein to 15a involved in the present invention, and the successful intercalation of triolein into acetic acid Characterization diagram of the fibrous membrane.

4I and II are diagrams of the adsorption process of polycyclic aromatic hydrocarbons by triolein-embedded multivesicular magnetic nanoparticles involved in the present invention.

4 III, IV and V are schematic diagrams of separating and eluting pollutants by using an external magnetic field in the present invention.

Figure 4VI is a schematic diagram of the determination and analysis of polycyclic aromatic hydrocarbons by GC/UPLC-MS involved in the present invention.

detailed description:

The present invention will be further described in detail below in conjunction with the accompanying drawings and examples.

Example:

The preparation process of triolein-embedded multivesicular magnetic nanoparticles involved in this example, with the help of the rapid separation performance of magnetic nanomaterials under an external magnetic field, has similar adsorption kinetics of biological water hydrophobic pollutants to its surface coating The characteristic triolein cellulose acetate composite membrane particles, the specific preparation steps are:

(1) Co-precipitation method to synthesize Fe ₃ O ₄ MNPs aqueous solution: 2.0g FeCl ₂ 4H ₂ O and 5.2g FeCl ₃ 6H ₂ O were dissolved in 25ml of oxygen-free deionized water, and 0.85mL of concentrated hydrochloric acid was added to form a mixed solution , under nitrogen protection and constant stirring, the mixed solution was added dropwise to 250mL 1.5M NaOH solution to obtain Fe ₃ O ₄ MNPs, and Fe ₃ O ₄ MNPs were washed with 200mL deionized water for 5-10 times, and then suspended and stored in In 220mL of deionized water, an aqueous solution of Fe ₃ O ₄ MNPs with a concentration of 10mg/mL and a particle size of 10nm was prepared;

(2) Preparation of emulsion: add cellulose acetate with a concentration of 0.02g/mL and triolein with a concentration of 0.2g/mL into 25mL of acetone to form a mixture, place the sealed mixture on a shaker at 100r /min shake for 1-9 hours, make it fully mixed, and complete the preparation of the emulsion;

(3) Preparation of Fe ₃ O ₄ @CTAB MNPs: Take 10 mL of the Fe ₃ O ₄ MNPs solution synthesized in step (1) and add it to 10 mL of cetyltrimethylammonium bromide (CTAB) aqueous solution with a concentration of 5 mg/mL A mixed solution was formed in the mixture, and the mixed solution was sonicated for 10-15min at room temperature, so that the surface of Fe ₃ O ₄ MNPs was fully modified by CTAB, and Fe ₃ O ₄ @CTABMNPs with a radial structure on the hydrophobic surface were obtained, which were electrostatically adsorbed by CTAB cationic terminals On the surface of Fe3O4@CTAB MNPs magnetic nanomaterials;

(4) Preparation of emulsified Fe ₃ O ₄ @CTAB MNPs: Heat the water bath to 35±2°C, and mechanically stir at 300r/min, add the Fe ₃ O ₄ @CTAB MNPs prepared in step (3) dropwise A mixed solution is formed in the emulsion prepared in step (2), and 50 ml of NaOH aqueous solution with a pH value of 10.0 is added dropwise to the mixed solution to obtain emulsified Fe ₃ O ₄ @CTAB MNPs;

(5) Preparation of triolein-embedded multivesicular magnetic nanoparticles: Concentrate the emulsified Fe ₃ O ₄ @CTABMNPs prepared in step (4) to a viscous state with a rotary evaporator at a temperature of 28-32°C and freeze-dry , Fe ₃ O ₄ @Triolein@CAMMNPs were obtained, and Fe ₃ O ₄ @Triolein@CAM MNPs were soaked in deionized water at 10°C for 12 hours to obtain triolein-embedded multivesicular magnetic nanoparticles.

The specific performance of the embedded triolein multivesicular magnetic nanoparticles involved in this example in simulating, detecting and analyzing the concentration distribution of environmental pollutants, and testing the adsorption kinetics and biological effectiveness of animal cells to hydrophobic pollutants The process steps are:

(1) First, 1 to 2 parts by weight of embedded triolein multivesicular magnetic nanoparticles are placed in the water to be tested, stirred for 5 to 10 minutes, and mixed uniformly to form a mixed solution;

(2), then the mixed solution was left to stand for 3 hours and the nanoparticles were separated with a magnet, and the supernatant was poured out;

(3) According to the volume ratio of 1:3, take 20mL of acetonitrile and 60mL of n-hexane and stir to form a mixed solution. The mixed solution is ultrasonically cleaned for 10min with 5mL each time to elute the organic pollutants enriched on the nanoparticles, and 20mL containing the target compound eluent;

(4) Concentrate the eluate obtained in step (3) with a nitrogen blower, and set the volume to 1ml, then filter it into a 1.5mL liquid phase bottle with a 0.22 μm glass fiber filter membrane, and use GC/UPLC- MS detects PAHs (polycyclic aromatic hydrocarbons); add triolein-embedded multivesicular magnetic nanoparticles to 1L of water containing 100ng/L acrylic pyrene, and enrich for 48 hours under slow stirring. Samples were taken at 0.5, 1, 2, 4, 8, 16, 24, 36 and 48, respectively, and the amount of enriched PAHs was detected. After the kinetic experiment analysis, it was shown that the embedded triolein multivesicular magnetic nanoparticles had a positive effect on the water body. The adsorption kinetics of PAHs gradually reaches saturation with the increase of time, which has the kinetic characteristics of the adsorption of pollutants by aquatic organisms.

Claims (1)

1. the preparation method of many vesica magnetic nanoparticles of a kind of embedded triolein, it is characterised in that preparation technology receives by magnetic The performance of rice material quick separating under externally-applied magnetic field, has similar biological to the suction of water body hydrophobic contaminant to its pan coating The triolein cellulose acetate composite film particle of attached dynamic characteristic, its specific preparation process is：

(1), Co deposited synthesis Fe₃O₄The MNPs aqueous solution：By 2.0g FeCl₂·4H₂O and 5.2gFeCl₃·6H₂O is dissolved in In 25ml anaerobic deionized waters, and add 0.85mL concentrated hydrochloric acids to form mixed liquor, in the case where nitrogen is protected and is stirred continuously, will mix Liquid is added dropwise to obtain Fe in the NaOH solution of 250mL1.5M₃O₄MNPs, Fe is cleaned with 200mL deionized waters₃O₄ MNPs5-10 is suspended after and is stored in the deionized water of 220mL, concentration is obtained for 10mg/mL and particle diameter is 10nm's Fe₃O₄The MNPs aqueous solution；

(2) emulsion, is prepared：By concentration for the triolein that the cellulose acetate and concentration of 0.02g/mL are 0.2g/mL is added into Mixture is formed in 25mL acetone, the mixture after sealing is placed on oscillator and is vibrated 1-9 hours with 100r/min, fill it Divide and mix, complete the preparation of emulsion；

(3) Fe, is prepared₃O₄@CTAB MNPs：Take the Fe of 10mL steps (1) synthesis₃O₄MNPs solution is added to 10mL concentration Mixed liquor is formed in the CTAB aqueous solution of 5mg/mL, ultrasonic mixing liquid 10-15min, makes Fe at room temperature₃O₄MNPs surfaces are by CTAB Fully modification, obtains the Fe of the radial structure with hydrophobic surface₃O₄@CTAB MNPs, it is quiet by CTAB cations termination Electro Sorb is in Fe₃ The surface of O4@CTAB MNPs magnetic Nano materials；

(4) emulsification Fe, is prepared₃O₄@CTAB MNPs：Water-bath is heated to 35 ± 2 DEG C, and with the mechanical agitation of 300r/min, Fe prepared by step (3)₃O₄@CTAB MNPs are added dropwise over forming mixed liquor in the emulsion of step (2) preparation, in mixed liquor In be added dropwise over the NaOH aqueous solution 50mL that pH value is 10.0, obtain emulsify Fe₃O₄@CTAB MNPs；

(5) many vesica magnetic nanoparticles of embedded triolein, are prepared：By the obtained emulsification Fe of step (4)₃O₄@CTAB MNPs are used It is thick and cold dry that rotary evaporator controls 28~32 DEG C of temperature to be concentrated into, and obtains Fe₃O₄@Triolein@CAM MNPs, then use 10 DEG C of deionized water immersion Fe₃O₄@Triolein@CAM MNPs 12 hours, obtain many vesica magnetic Nanos of embedded triolein Grain；Prepare many vesica magnetic nanoparticles of embedded triolein be applied to simulate, detect and analysis environments concentration distribution of pollutants, To the adsorption dynamics adsorption kinetics behavior of hydrophobic contaminant and biological effectiveness, concrete technology step is inspection zooblast：

(1), first many vesica magnetic nanoparticles of the embedded triolein of 1~2 weight portion are placed in tested water, 5~10 points are stirred Clock, is well mixed it and forms mixed liquor；

(2) nano particle and then after mixed liquor is stood into 3 hours is isolated with magnet, supernatant is poured out；

(3), according to 1:3 volume ratio takes acetonitrile 20mL and n-hexane 60mL and stirs to form mixed liquor, by mixed liquor with each 5mL The organic pollution for being cleaned by ultrasonic 10min to be enriched with eluting nano-particles, obtains the eluent that 20mL contains target compound；

(4) eluent that step (3) is obtained is concentrated with Nitrogen evaporator, and is settled to 1mL, then with 0.22 μm of glass Fibrous filter membrane is filtered into 1.5mL liquid phases bottle, and PAHs is detected with GC/UPLC-MS；By many vesica magnetic of embedded triolein Nano particle is added in the water body that 1L contains 100ng/L propyl benzene pyrenes, under low rate mixing, is enriched with 48 hours, in 0.25,0.5,1, 2nd, 4,8,16,24,36 and 48 when it is separately sampled, detect enrichment PAHs amount, show after carrying out analysis for kinetics, embed three The many vesica magnetic nanoparticles of olein are increased over time to the absorption power of PAHs in water body, and progressively reach saturation, tool There is the dynamic characteristic adsorbed to pollutant with aqueous bio.