CN111229189B - Self-assembly type amino acid derivative functionalized magnetic-carbon nanotube composite material and preparation method and application thereof - Google Patents
Self-assembly type amino acid derivative functionalized magnetic-carbon nanotube composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a self-assembly type amino acid derivative functionalized magnetic-carbon nanotube composite material, a preparation method and application thereof, and magnetic Fe is prepared by utilizing a solvothermal reduction one-step method3O4-multi-walled carbon nanotube composites, using magnetic Fe3O4The MWCNTs composite material has the hydrophobic effect, N-hexadecyl-L-hydroxyproline is self-assembled on the surface of a carbon nano tube to obtain a stable compound, and the material is used as a chiral adsorbent to separate amino acid enantiomers so as to test the chiral separation performance of the material. The invention takes the magnetic nano material as the chiral selector carrier and combines the self-loading technology as a fixing mode to prepare the chiral identification material, thereby being hopeful to improve the defects of the stability and the loading capacity of the chiral stationary phase, realizing the rapid screening of the chiral selector and the efficient and high-capacity chiral separation.
Description
Technical Field
The invention belongs to the technical field of functional materials and chiral separation, and particularly relates to a self-assembly type amino acid derivative functionalized magnetic-carbon nanotube composite material, a preparation method thereof and application thereof in chiral separation.
Background
The two enantiomers of a chiral compound have the same physical and chemical properties except for optical rotation, but the biochemical and pharmacological activities are often different and even have opposite effects. Therefore, the research on the chiral separation technology has very important significance for the medical industry and the life science. The chiral resolution technology mainly comprises various resolution methods such as mechanical resolution, preferential crystallization, chemical resolution, enzyme resolution, membrane separation, chromatographic resolution and the like. Among them, the liquid chromatography chiral stationary phase resolution method is considered to be the most advantageous optical isomer resolution method, and various chiral stationary phases have been developed so far, and can be classified into a protein type, a brush type/Prikle type, a polysaccharide derivative type, a macrocyclic antibiotic type, a ligand exchange type, a cyclodextrin type, and the like, according to the structure of the chiral stationary phase. The fixing mode of the chiral selector on the carrier can be divided into bonding type and coating type. With the development of modern science and technology, people know different biological activities of chiral compounds more and more deeply, the demand of single enantiomer is increased continuously, and the requirement of purity is higher and higher. Although the conventional chromatographic chiral separation technology has wide application, mild operation condition and high separation efficiency, the conventional chromatographic chiral separation technology has small treatment capacity and high amplification cost, and is mostly suitable for analysis and detection. Therefore, the research on novel chiral identification materials and high-efficiency and rapid chiral separation technology has wide application prospect. However, the development of chiral separation technology focuses more on the research of new materials in new technologies, and the fixing mode of the chiral selector on the carrier is mainly a bonding type and a coating type. The bonding type fixing mode has strong acting force and high stability, but the reaction process is complex and is not easy to reach higher bonding rate, and the chiral selector structure is easy to damage, so that the acting sites are reduced. The coating type fixing mode has simple operation, high coating amount and capacity of effectively improving the separation capacity, but is unstable, short in service life and easy to lose along with the flowing phase, so that the separation efficiency is reduced.
The research of the nano material becomes the leading research subject in the world at present, the nano material has wide application in the field of analytical chemistry and shows attractive application prospect in the field of chiral recognition. The nano-particles have high specific surface and are easy to modify, and can play a role in improving the column capacity or amplifying signals when being used as a chiral selector carrier. The research of the nano materials in the field of chiral recognition gets more and more attention, but the application range of the nano materials is greatly limited due to the defect that the solid-liquid separation of most nano materials in a solution is difficult to realize. The magnetic nano-particles have the characteristics of small size effect, surface effect and the like which are peculiar to nano-materials, have unique magnetic properties, can be rapidly aggregated under the action of an external magnetic field so as to realize solid-liquid separation, and are widely applied to the fields of catalysis, biological separation, medicine and the like [17-18 ]. Research on the preparation and application of novel functionalized magnetic nano materials and composite materials thereof has attracted the wide interest of researchers. In recent years, functionalized magnetic nano prepared by modifying a chiral selector on the surface has great application potential in the field of chiral separation.
Self-assembly refers to a process of spontaneously forming an ordered structure by a non-covalent bond function of a structural element (such as a molecule) of a system without the help of an external force, is an important way for creating a new material with a multilayer structure and functions, and is the field of international leading-edge study. The molecular self-assembly technique forms ordered molecular aggregates such as self-assembled films by virtue of weak intermolecular interaction including hydrogen bonding, van der waals forces, hydrophobic interactions, pi-pi interactions, cation-pi interactions, and the like, and synergistic effects thereof. Carbon nanotubes are a new material that has been rapidly developed in recent years, and are widely used in the field of analytical chemistry because of their properties such as large surface area and hydrophobic surface. Magnetic carbon nanotube composites are typically made of magnetic Fe3O4Or gamma-Fe2O3And single-walled carbon nanotubes (SWCNTs) or multi-walled carbon nanotubes (MWCNTs). The composite material combines the super paramagnetic performance of the magnetic nano particles and the unique optical, electrical, mechanical and chemical properties of the carbon nano tubes, thereby being widely applied to the fields of sensing, biological separation, sample pretreatment and the like.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a self-assembly type amino acid derivative functionalized magnetic-carbon nanotube composite material, and a preparation method and application thereof, prepares a chiral identification material by taking a magnetic nano material as a chiral selector carrier and combining an automatic assembly technology as a fixing mode, is expected to improve the defects of the stability and the loading capacity of a chiral stationary phase, realizes the rapid screening of a chiral selector, and has high efficiency and high capacity chiral separation.
Magnetic Fe is prepared by a solvothermal reduction one-step method3O4Multiwalled carbon nanotubes (Fe)3O4MWCNTs) composite material using magnetic Fe3O4The hydrophobic effect of the MWCNTs composite material is that N-hexadecyl-L-hydroxyproline (C16-L-Hyp) is self-assembled on the surface of the carbon nano tube to obtain stable compound Fe3O4MWCNTs-Hyp. The material is used as a chiral adsorbent to resolve the enantiomers of the amino acid so as to test the chiral resolving performance of the material.
The technical purpose of the invention is realized by the following technical scheme.
The self-assembly type amino acid derivative functionalized magnetic-carbon nanotube composite material is prepared by the following steps:
step 1, preparing magnetic Fe by using solvothermal reduction one-step method3O4-multi-walled carbon nanotube composite
Weighing FeCl3·6H2Adding O into ethylene glycol to prepare a solution of 0.05-0.4 mol/L; then adding anhydrous sodium acetate, polyethylene glycol and carboxylated multi-walled carbon nanotubes into the mixture for ultrasonic dispersion; adding an amination reagent after ultrasonic dispersion, mechanically stirring, transferring the liquid into a reaction kettle, heating to 200-300 ℃ and reacting for 8-24 h, wherein FeCl3·6H2The mass ratio of O, anhydrous sodium acetate, polyethylene glycol, the carboxylated multi-walled carbon nanotube and the amination reagent is (1-1.5): (3.5-4): (0.8-1): (0.1-0.5): (6-20), the amination reagent is hexamethylene diamine or ethylene diamine;
in step 1, the reaction kettle is a sealed stainless steel hydrothermal reaction kettle with a polytetrafluoroethylene lining.
In step 1, the polyethylene glycol is PEG 6000.
In the step 1, washing a product obtained after the reaction for 3-6 times by using deionized water and absolute ethyl alcohol, and drying in vacuum at 40-80 ℃ to obtain the amino modified magnetic Fe3O4-carbon nanotube composites.
In the step 1, the ultrasonic dispersion time is 0.5-1 h, the mechanical stirring time is 0.5-1 h, and the stirring speed is 80-120 r/min.
In step 1, the reaction temperature is 240-280 ℃, the reaction time is 10-20 hours, and FeCl3·6H2The mass ratio of O, anhydrous sodium acetate, polyethylene glycol, the carboxylated multi-walled carbon nanotube and the amination reagent is (1-1.5): (3.5-4): (0.8-1): (0.3-0.5): (10-15).
In step 2, N-hexadecyl-L-hydroxyproline is uniformly dispersed in methanol and added with the magnetic Fe prepared in step 13O4The multi-wall carbon nano tube composite material is stirred uniformly and then stands still (for example, stands still for 30-60 min at the room temperature of 20-25 ℃) to realize self-assembly; removing methanol by magnetic separation, and separating self-assembled amino acid derivative Fe3O4Adding the MWCNTs composite material into 10ml of 50 mmol.L-1CuSO4Stirring for 10min in water solution, removing solution by magnetic separation, washing with distilled water for 3-5 times, and vacuum drying at 80 deg.C to obtain dried self-assembled amino acid derivative functionalized magnetic-carbon nanotube composite material.
In step 2, N-hexadecyl-L-hydroxyproline was prepared according to the following procedure: adding sodium hydroxide and L-hydroxyproline into acetonitrile, uniformly dispersing, adding bromohexadecane, carrying out reflux reaction for 5-10 hours at 60-80 ℃, carrying out rotary evaporation to obtain a white solid product, recrystallizing with methanol twice, carrying out suction filtration, and carrying out vacuum drying at 60 ℃ to obtain N-hexadecyl-L-hydroxyproline (C16-L-Hyp), wherein the molar ratio of the sodium hydroxide, the L-hydroxyproline and the bromohexadecane is equal.
Compared with the prior art, the invention has the advantages that: (1) by solvothermal one-stage processReacting to obtain amino modified magnetic Fe3O4The nano particle-carbon nano tube composite material has simple preparation method and controllable process, and the reaction is based on the coordination of amino and iron ions and the electrostatic assembly effect with the carbon nano tube, so that the composite material has tighter binding force and stable property and is not easy to separate under the ultrasonic condition; (2) magnetic Fe obtained3O4The MWCNTs composite material has nano size and superparamagnetism, can be stably dispersed in a solution, and can realize rapid separation and enrichment by adopting the action of a simple magnetic field; (3) the magnetic composite material has large surface area and various functionalized active sites on the surface, and can be used as an adsorbent to self-assemble amino acid derivatives through pi-pi electronic interaction and hydrophobic interaction of the carbon nano tube; (4) the magnetic separation technology using the magnetic nano particles as the adsorbent has the advantages of simplicity, rapidness, high efficiency and the like; magnetic nano particles are introduced as carriers, so that further modification and surface loading capacity increase are facilitated, more host and guest action sites are provided, and the chiral separation capacity is increased; and the magnetic field separation technology is used for replacing the traditional separation technology, so that the separation and the regeneration can be quickly realized. The introduction of magnetic nanoparticles has a major effect on chiral separation of three points: the magnetic nanoparticles have small particle size and large surface area, and can be used as a carrier to increase the loading capacity; secondly, the magnetic nanoparticles are easy to modify on the surface, thereby being beneficial to realizing controllable design; thirdly, the selective separation of the target object and the simple regeneration of the adsorbent are realized by switching the magnetic field, and the service life of the adsorbent can be prolonged. Compared with the traditional chiral analysis technology, the method has the advantages that the magnetic nanoparticle loaded chiral main body is introduced to construct the chiral separation system, so that the rapid and efficient separation can be realized. (5) Loading chiral main body molecules on the surface of the functionalized magnetic nano material by utilizing an autonomous loading technology, thereby preparing a multifunctional magnetic composite material with chiral recognition capability and magnetism; through the synergistic effect of interaction forces such as electrostatic attraction, hydrophobicity, coordination and the like, the chiral main body is loaded on the surface of the functionalized magnetic nano material in a self-assembly mode. The chiral main body molecules are self-assembled into the functionalized magnetism by taking the self-assembly technology and the nano science as tractionAnd (3) a composite material surface. The dynamic ordered self-assembly method can effectively avoid the phenomena of disordered spatial arrangement, uneven distribution and the like and is beneficial to large-scale preparation; and according to the molecular structure characteristics of the chiral main body, the chiral main body is loaded on the surface of the magnetic material in a self-assembly mode, so that the method is simple, the loading capacity is high, and the method has a huge application prospect.
Drawings
FIG. 1 is a transmission electron micrograph of a magnetic material of the present invention in which (a) magnetic Fe3O4Nanoparticles, (b) magnetic Fe3O4The MWCNTs composite material.
FIG. 2 is an XRD spectrum diagram of a magnetic material of the present invention in which (a) magnetic Fe3O4Nanoparticles, (b) magnetic Fe3O4The MWCNTs composite material.
FIG. 3 is a hysteresis loop test spectrum of the magnetic material of the present invention, wherein (a) magnetic Fe3O4Nanoparticles, (b) magnetic Fe3O4MWCNTs composite material, (c) magnetic Fe3O4The MWCNTs-Hyp composite material.
FIG. 4 is a FT-IR spectrum of a magnetic material of the present invention in which (a) magnetic Fe3O4MWCNTs composite material, (b) magnetic Fe3O4a/MWCNTs-Hyp composite material, (C) C16-L-Hyp.
Detailed Description
The technical scheme of the invention is further explained by combining specific examples. Magnetic Fe in connection with the present invention3O4The preparation of the MWCNTs composite material and hexadecyl-L-hydroxyproline can refer to the prior art, such as Chinese invention patent 'a magnetic carbon nanotube composite material, a preparation method and an application thereof', the application number is 201210514808.2, and the application date is 12 months and 4 days 2012.
Example 1 preparation of self-assembled hexadecyl-L hydroxyproline functionalized magnetic-carbon nanotube composite
(1) Magnetic Fe3O4Preparation of MWCNTs composite material
1.35g FeCl was weighed3·6H2O was added to 35mL of ethylene glycol solution. Then 3.6g of anhydrous sodium acetate, 1.0g of polyethylene glycol and 0.2g of carboxylated multi-walled carbon nano-tube are added in sequence, and ultrasonic dispersion is carried out for 0.5 h. Adding 6mL of hexamethylene diamine, continuously mechanically stirring for 0.5h, transferring the liquid into a sealed stainless steel hydrothermal reaction kettle with a polytetrafluoroethylene lining, and heating to 220 ℃ for reaction for 8 h. Washing the obtained product with deionized water and anhydrous ethanol for 6 times, and vacuum drying at 80 deg.C to obtain magnetic Fe3O4The MWCNTs composite material.
(2) Preparation of self-assembly type amino acid derivative functionalized magnetic-carbon nanotube composite material
1.38g (10mmol) NaOH and 1.31g (10mmol) L-hydroxyproline were added to a three-necked flask containing 10ml acetonitrile, 3.05g (10mmol) bromohexadecane was added with stirring, refluxed at 80 ℃ for 8hr, and rotary evaporated to give the product as a white solid. Recrystallizing twice with methanol, filtering, and vacuum drying at 60 deg.C to obtain N-hexadecyl-L-hydroxyproline (C16-L-Hyp).
The N-hexadecyl amino acid derivative was weighed and dissolved in 10ml of methanol. Adding Fe into the solution3O4The MWCNTs composite material is stirred uniformly and then stands for 30min, and methanol is removed by magnetic separation. Fe to self-assemble amino acid derivatives3O4Adding the MWCNTs composite material into 10ml of 50mmol/L CuSO4Stirring for 10min, and removing the solution by magnetic separation. Washing with distilled water for 3-5 times, and vacuum drying at 80 deg.C to obtain magnetic Fe3O4The MWCNTs-Hyp composite material.
Example 2 structural characterization of magnetic materials
(1) Morphology and size characterization
The particle size and morphology of the prepared magnetic particles were observed with a transmission electron microscope (FEI, usa) of Tecnai G2F20 type. FIG. 1 shows magnetic Fe3O4Nanoparticles and magnetic Fe3O4Transmission electron microscope photo of/MWCNTs-Hyp composite material. From FIG. 1(a), it can be seen that the magnetic Fe without the multi-walled carbon nanotube3O4The nano particles are petal-like, and the particle size is 80 +/-5 nm; FIG. 1(b) shows magnetic Fe3O4Magnetic Fe in/MWCNTs-Hyp composite material3O4The nano particles are uniformly deposited on the carbon nano tubes, the particle size is 60 +/-5 nm, and after the carbon nano tubes are added, the steric hindrance is increased, so that the crystal nucleus growth is limited, and the magnetic Fe is enabled3O4The particle size of the nano particles is reduced.
(2) Crystal form characterization
The crystal type of the magnetic microspheres, magnetic Fe, was characterized by Rigaku D/max 2500X-ray diffractometer (Nippon Denko Co., Ltd.)3O4Nanoparticles and magnetic Fe3O4The XRD spectrum of the/MWCNTs-Hyp composite material is shown in figure 3. Magnetic Fe, as can be seen in contrast to X-ray diffraction cards3O4The crystal structure of the nano particles is spinel, and after the nano particles are compounded with the carbon nano tubes, Fe3O4The number of diffraction peaks was not increased and the position was not changed, but a diffraction peak of carbon appeared at 26.2 ° 2 θ, indicating that magnetic Fe was present during the recombination process3O4The crystal form of the particles is not changed.
(3) Magnetic characterization
The magnetic properties of the magnetic material were characterized using a physical property measurement system of the PPMS-9 type (Quantum Design, USA). Magnetic Fe3O4Nanoparticles, magnetic Fe3O4MWCNTs composite material and magnetic Fe3O4The hysteresis loop of the MWCNTs-Hyp composite is shown in FIG. 3. Magnetic Fe3O4Nanoparticles, magnetic Fe3O4MWCNTs composite material and magnetic Fe3O4The remanence and the coercive force of the/MWCNTs-Hyp composite material both tend to zero, and the composite material is represented as superparamagnetism. Since MWCNTs and C16-L-Hyp have no magnetic response performance, Fe3O4The saturation magnetization is reduced after the compound is compounded with MWCNTs and C16-L-Hyp. The saturation magnetization is 75.5, 54.1 and 47.1emu g respectively-1。
(4) Functional group characterization
A Nicolet 6700 type Fourier infrared spectrometer (ThermoFisher company in America) is adopted to characterize the functional group change of the magnetic material, namely magnetic Fe3O4MWCNTs composite material, C16-L-Hyp, magnetic Fe3O4The Fourier infrared spectrogram (FT-IR) of the/MWCNTs-Hyp composite material is shown in FIG. 4. From FIG. 4, magnetic Fe can be seen3O4The MWCNTs-Hyp composite material is in 2846 cm and 2915cm-1The absorption peak at-C-H is enhanced and is the-CH of C16-L-Hyp2Radical generation, indicating the success of surface amino acid self-assembly (using the hydrophobic interaction of hexadecyl and carbon nanotubes); in addition, at 1581cm-1An absorption peak of C ═ O occurs, which is generated by the carboxyl groups on the multi-walled carbon nanotubes.
Example 3 self-assembled hexadecyl-L hydroxyproline functionalized magnetic-carbon nanotube composite for amino acid resolution
The self-assembly type amino acid derivative functionalized magnetic-carbon nanotube composite material prepared by the technical scheme of the invention is used for resolving amino acid chiral isomers. With magnetic Fe3O4The MWCNTs-Hyp composite material is used as a chiral adsorbent, and an amino acid enantiomer in a solution is resolved to test the chiral resolution capability of the MWCNTs-Hyp composite material, wherein a functional group L-hydroxyproline is a chiral ligand for realizing chiral recognition. The chiral ligand is coordinated with D-and L-enantiomers of amino acid respectively through central metal ions to form complexes of two diastereomers, and the two complexes have different stabilities, thereby realizing chiral separation.
DL-phenylalanine was selected as the analyte and the resolution effect was analyzed by HPLC. A standard solution with phenylalanine mass concentration of 10. mu.g/L was prepared from acetonitrile-water (volume ratio 7:3) and subjected to liquid chromatography (instrument model Shimazu HPLC-20A, Shimadzu corporation, Japan Shimadzu corporation, SPD-M20A type diode array detector, CTO-20AC column incubator, SIL-20AC autosampler, chromatographic conditions were chiral Spursil C18 column (250 mm. times.4.6 mm I.D,5.0 μ M particles), Beijing Dike Mac technology Co., Ltd., mobile phase acetonitrile, water, triethylamine (volume ratio 70:30:0.4), flow rate 1mL min -120 mu L of sample introduction amount and 254nm of detection wavelength) to obtain the peak areas of two enantiomers of phenylalanine before chiral adsorption.
Taking 100mg of magnetismFe3O4the/MWCNTs-Hyp composite material is placed in a 10mL centrifuge tube; preparing C16-L-hydroxyproline aqueous solution with the concentration of 10 mu g/L, adding copper sulfate with the concentration of 10mmol/L, and adjusting the pH value to 5.5 by phosphoric acid. 1mL of magnetic Fe3O4The MWCNTs-Hyp composite material is uniformly mixed and oscillated for 2h, and solid-liquid separation is carried out under the assistance of an external magnetic field. Taking 100 mu L of supernatant, adding acetonitrile/triethylamine/water (70:0.4:30) solution containing 10mmol of 2,3,4, 6-tetra-O-acetyl-beta-D-glucose isothiocyanate as a pre-column chiral derivatization reagent, filtering by using a 0.22 mu m water washing filter membrane, and taking 20 mu L of the solution each time to carry out liquid chromatography analysis so as to determine the content ratio of two enantiomers of the amino acid after the solution reacts with the magnetic material.
The chiral separation result shows that before the magnetic material acts, the DL-phenylalanine enantiomer solution contains equal amount of enantiomer, and the peak areas of the two enantiomers are almost equal. After the magnetic material is mixed and acted, the peak areas of two enantiomers in the supernatant are obviously reduced, wherein the reduction amount of the peak area of the L-enantiomer is larger than that of the peak area of the D-enantiomer, the ratio of the peak areas of the two enantiomers is D: L-56: 44, and the enantiomeric excess (ee) value is 12%, which indicates that the magnetic material selectively identifies the two enantiomers, and the acting force on the L-enantiomer is larger than that of the D-enantiomer, so that the content of the D-enantiomer in the supernatant after magnetic separation is larger than that of the L-enantiomer.
The preparation of the self-assembled hexadecyl-L-hydroxyproline functionalized magnetic-carbon nanotube composite material can be realized by adjusting the process parameters according to the content of the invention, and the performance basically consistent with the invention is shown, namely the application of the self-assembled amino acid derivative functionalized magnetic-carbon nanotube composite material in chiral separation of phenylalanine. The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (5)
1. Self-assembly typeThe application of the amino acid derivative functionalized magnetic-carbon nanotube composite material in chiral separation of phenylalanine is characterized in that the self-assembled amino acid derivative functionalized magnetic-carbon nanotube composite material is prepared by utilizing a solvothermal reduction one-step method to prepare magnetic Fe3O4Multiwalled carbon nanotube composites using magnetic Fe3O4Self-assembling N-hexadecyl-L-hydroxyproline on the surface of the carbon nanotube by virtue of the hydrophobic effect of the multi-wall carbon nanotube composite material according to the following steps:
step 1, preparing magnetic Fe by using solvothermal reduction one-step method3O4-multi-walled carbon nanotube composite
Weighing FeCl3·6H2Adding O into ethylene glycol to prepare a solution of 0.05-0.4 mol/L; then adding anhydrous sodium acetate, polyethylene glycol and carboxylated multi-walled carbon nanotubes into the mixture for ultrasonic dispersion; adding an amination reagent after ultrasonic dispersion, mechanically stirring, transferring the liquid into a reaction kettle, heating to 200-300 ℃ and reacting for 8-24 h, wherein FeCl3·6H2The mass ratio of O, anhydrous sodium acetate, polyethylene glycol, the carboxylated multi-walled carbon nanotube and the amination reagent is (1-1.5): (3.5-4): (0.8-1): (0.1-0.5): (6-20), the amination reagent is hexamethylene diamine or ethylene diamine;
step 2, the magnetic Fe prepared in the step 1 is used3O4The multi-wall carbon nanotube composite material and the N-hexadecyl-L-hydroxyproline act to realize the effect of the N-hexadecyl-L-hydroxyproline on the magnetic Fe through the hydrophobic effect of the two3O4Self-assembling on the multi-wall carbon nano tube composite material to obtain the self-assembled amino acid derivative functionalized magnetic-carbon nano tube composite material.
2. The application of the self-assembled amino acid derivative functionalized magnetic-carbon nanotube composite material in chiral separation of phenylalanine according to claim 1, wherein in the step 1, the reaction kettle is a sealed stainless steel hydrothermal reaction kettle with a polytetrafluoroethylene lining, and the polyethylene glycol is PEG 6000.
3. The application of the self-assembled amino acid derivative functionalized magnetic-carbon nanotube composite material in chiral separation of phenylalanine according to claim 1, wherein in the step 1, the reaction temperature is 240-280 ℃, the reaction time is 10-20 hours, and FeCl is added3·6H2The mass ratio of O, anhydrous sodium acetate, polyethylene glycol, the carboxylated multi-walled carbon nanotube and the amination reagent is (1-1.5): (3.5-4): (0.8-1): (0.3-0.5): (10-15); the ultrasonic dispersion time is 0.5-1 h, the mechanical stirring time is 0.5-1 h, and the stirring speed is 80-120 r/min.
4. The application of the self-assembled amino acid derivative functionalized magnetic-carbon nanotube composite material in chiral separation of phenylalanine according to claim 1, wherein in step 2, N-hexadecyl-L-hydroxyproline is uniformly dispersed in methanol and added with the magnetic Fe prepared in step 13O4And (3) uniformly stirring the multi-wall carbon nano tube composite material, standing the mixture at room temperature of 20-25 ℃ for 30-60 min, and realizing self-assembly.
5. The application of the self-assembled amino acid derivative functionalized magnetic-carbon nanotube composite material in chiral separation of phenylalanine according to claim 1, wherein in the step 2, the N-hexadecyl-L-hydroxyproline is prepared according to the following steps: adding sodium hydroxide and L-hydroxyproline into acetonitrile, uniformly dispersing, adding bromohexadecane, carrying out reflux reaction for 5-10 hours at 60-80 ℃, carrying out rotary evaporation to obtain a white solid product, recrystallizing with methanol twice, carrying out suction filtration, and carrying out vacuum drying at 60 ℃ to obtain N-hexadecyl-L-hydroxyproline, wherein the molar ratio of the sodium hydroxide, the L-hydroxyproline and the bromohexadecane is equal.
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