CN113201148A - Spiral infinite ordered growth COFs material and preparation method and application thereof - Google Patents
Spiral infinite ordered growth COFs material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a spiral infinite ordered growth COFs material, wherein reaction monomers of the COFs material comprise rigid aromatic aldehyde monomers and flexible aliphatic amine monomers; also discloses a preparation method of the spiral infinite ordered growth COFs material, and also discloses an application of the spiral infinite ordered growth C OFs material; the COFs material growing in a spiral infinite order has large adsorption capacity on food sample matrixes, the preparation method is simple, the reaction process and the number of spiral rings in the preparation process are controllable, the COFs material can be used for analyzing quinolone drug residues in reaction food samples and realizing one-step separation and purification, the sample pretreatment efficiency is greatly improved, and the analysis time is shortened.
Description
Technical Field
The invention relates to the technical field of preparation of food chemical functional materials, in particular to a spiral COFs material capable of infinitely and orderly growing as well as a preparation method and application thereof.
Background
Quinolone drugs are used for preventing and treating infectious diseases as a broad-spectrum antibiotic and are largely used in animal husbandry, trace quinolone drugs left in livestock, aquatic products and egg products potentially promote the formation of drug-resistant bacteria and even super multi-drug-resistant bacteria, and further bring harm to human endocrine systems, so that the rapid determination of the video heavy quinolone drug residues is the most important factor for monitoring food chemical pollutants.
In recent years, with the development and popularization of mass spectrometry technology, liquid chromatography tandem mass spectrometry has become a gold standard for detecting video heavy quinolone drug residues, and in order to meet the requirement of mass spectrometry on sample purification, a passage-type solid phase extraction technology is increasingly concerned by broad scholars as a novel sample pretreatment technology, wherein sample extraction liquid can realize sample purification by flowing through a solid phase extraction column.
Covalent organic framework materials (COFs) are widely applied to the development of the passage-type solid phase extraction technology as a novel carbon nano material. At present, the effective synthesis of COFs materials is a difficult point and a hot point in the field. Because the monomers in the COFs are all connected by covalent bonds, the generation and extension of the constituent units need high activation energy, and in addition, the reaction conditions need to be precisely controlled in the reaction process to promote the good growth of the COFs crystals. In view of the strong adsorption capacity of the COFs material to impurities in food samples and the difficulty of effective synthesis of the COFs material, the preparation technology of the COFs with high yield, high quality and large specific surface area is developed and applied to one-step purification of the residual quinolone drugs in the food samples, so that the preparation technology has wide application prospects and certain challenges.
Disclosure of Invention
The invention aims to provide a spiral COFs material capable of growing in an unlimited and ordered manner, a preparation method and an application thereof aiming at the defects in the prior art, the spiral COFs material capable of growing in an unlimited and ordered manner has large adsorption capacity on a food sample substrate, the preparation method is simple, the reaction process and the number of spiral rings in the preparation process are controllable, the spiral COFs material can be used for analyzing quinolone drug residues in reaction food samples and realizing one-step separation and purification, the sample pretreatment efficiency is greatly improved, and the analysis time is shortened.
In order to solve the technical problems, the invention adopts the following technical scheme:
the spiral infinite ordered growth COFs material is characterized in that: the reactive monomers of the COFs material comprise rigid aromatic aldehyde monomers and flexible aliphatic amine monomers.
Optionally, the rigid aromatic aldehyde monomer is at least one of 4- (4-formylphenoxy) benzaldehyde, 1,3, 5-tri (formylphenyl) benzene, and 4,4' -biphenyldicarboxaldehyde.
Optionally, the flexible aliphatic amine monomer is at least one of diethylenetriamine, triethylenetetramine and tetraethylenepentamine.
The preparation method of the spiral infinite ordered growth COFs material is characterized by comprising the following steps: adding a reaction monomer of the COFs material into a polytetrafluoroethylene pressure-resistant bottle, and dispersing the reaction monomer for 10-30 min by using ultrasonic waves; transferring the polytetrafluoroethylene pressure-resistant bottle into a microwave reactor, and controlling the heating reaction process and the circulating heating reaction times by adopting a microwave program heating method; and after the heating reaction is finished, naturally cooling to room temperature, collecting filter residues by using a vacuum filtration method, leaching the filter residues by using dimethyl sulfoxide, acetone, ethanol and dichloromethane in sequence, and drying to obtain the spiral COFs with infinite and ordered growth.
Optionally, in the step of adding the reactive monomer of the COFs material into the polytetrafluoroethylene pressure-resistant bottle, 0.2-0.8 mmol of 1,3, 5-tri (p-formylphenyl) benzene, 0.6-2.4 mmol of tetraethylenepentamine, 5-10 mL of 1,3, 5-trimethylbenzene and 5-10 mL of 1, 4-dioxane are selected and added into the polytetrafluoroethylene thick-wall pressure-resistant bottle.
Optionally, the step of controlling the heating reaction process and the number of times of the cyclic heating reaction by using a microwave program heating method includes the following steps: the first stage is 6h, the temperature of the microwave reactor is increased from 40 ℃ to 80 ℃; in the second stage for 2 hours, the temperature of the microwave reactor is increased from 80 ℃ to 90 ℃, and the microwave reactor is kept at 90 ℃ for 4-16 hours; in the third stage of 6h, the temperature of the microwave reactor is reduced from 90 ℃ to 60 ℃; in the fourth stage, the temperature of the microwave reactor is increased from 60 ℃ to 100 ℃ and is kept at 100 ℃ for 4-16 h; in the fifth stage for 6h, the temperature of the microwave reactor is reduced from 100 ℃ to 60 ℃; in the sixth stage 6h, the temperature of the microwave reactor is increased from 60 ℃ to 120 ℃, and the temperature is kept at 120 ℃ for 12-24 h.
Optionally, the drying step includes the following step of drying the washed filter residue for 6-12 hours in a vacuum environment at 40-80 ℃.
The application of the spiral infinite ordered growth COFs material is characterized in that: weighing the homogenized food sample in a centrifuge tube, adding a proper amount of COFs material and acetonitrile, carrying out vortex centrifugation, and analyzing the supernatant by using an ultrafast liquid chromatography-tandem mass spectrometer.
Optionally, in the step of weighing the homogenized food sample in a centrifuge tube and adding a proper amount of the COFs material and acetonitrile, 2-8 parts by mass of the COFs material and 1-2 parts by mass of the acetonitrile are correspondingly added to every 200-400 parts by mass of the homogenized food sample.
Optionally, in the step of vortex centrifugation, vortex for 10-30 min, and centrifuging for 5-10 min at a rotating speed of 12000 r/min.
Compared with the prior art, the invention has the advantages that:
1) the preparation method is simple, and the reaction system can be heated uniformly by adopting a microwave method; the reaction process can be accurately controlled by adopting temperature programming, the infinite ordered growth of the COFs can be realized along with the gradual increase of the circulating reaction temperature, the synthesis efficiency of the COFs is greatly improved, and the prepared COFs with the spiral infinite ordered growth has high adsorption capacity, so that the high-efficiency adsorption of food sample impurities can be realized.
2) The invention realizes the controllable preparation of the spiral unlimited orderly growth COFs material, and the COFs material has strong removal capability on food sample matrixes, so that the COFs material is suitable for one-step separation and purification of quinolone drug residues in food samples; meanwhile, the method saves the sample pretreatment time and cost and has more advantages.
Drawings
FIG. 1 is a projection electron microscope of a helical infinite order growth COFs material according to an embodiment of the present invention;
FIG. 2 is an LC-MS/MS spectrum of the residue of a quinolone drug in a food product after purification in one embodiment of the present invention.
Detailed Description
Reference will now be made in detail to the exemplary embodiments, examples of which are illustrated in the accompanying drawings. When the following description refers to the accompanying drawings, like numbers in different drawings represent the same or similar elements unless otherwise indicated. The embodiments described in the following exemplary embodiments do not represent all embodiments consistent with the present invention. Rather, they are merely examples of apparatus and methods consistent with certain aspects of the invention, as detailed in the appended claims.
In the description of the present invention, it is to be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", and the like, indicate orientations and positional relationships based on those shown in the drawings, and are used only for convenience of description and simplicity of description, and do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be considered as limiting the present invention. Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more features. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; may be mechanically connected, may be electrically connected or may be in communication with each other; either directly or indirectly through intervening media, either internally or in any other relationship. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations. The technical features of the present invention may be combined with each other without conflict.
In the present invention, unless otherwise expressly stated or limited, "above" or "below" a first feature means that the first and second features are in direct contact, or that the first and second features are not in direct contact but are in contact with each other via another feature therebetween. Also, the first feature being "on," "above" and "over" the second feature includes the first feature being directly on and obliquely above the second feature, or merely indicating that the first feature is at a higher level than the second feature. A first feature being "under," "below," and "beneath" a second feature includes the first feature being directly under and obliquely below the second feature, or simply meaning that the first feature is at a lesser elevation than the second feature.
The following disclosure provides many different embodiments or examples for implementing different features of the invention. To simplify the disclosure of the present invention, the components and arrangements of specific examples are described below. Of course, they are merely examples and are not intended to limit the present invention. Furthermore, the present invention may repeat reference numerals and/or letters in the various examples, such repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed. In addition, the present invention provides examples of various specific processes and materials, but one of ordinary skill in the art may recognize applications of other processes and/or uses of other materials.
The invention relates to a spiral infinite ordered growth COFs material, wherein reaction monomers of the COFs material comprise rigid aromatic aldehyde monomers and flexible aliphatic amine monomers.
In some embodiments, the rigid aromatic aldehyde monomer is at least one of 4- (4-formylphenoxy) benzaldehyde, 1,3, 5-tris (formylphenyl) benzene, and 4,4' -biphenyldicarboxaldehyde.
In some embodiments, the flexible aliphatic amine monomer is at least one of diethylenetriamine, triethylenetetramine, tetraethylenepentamine.
In some embodiments, a method for preparing helical infinite ordered growth COFs materials comprises the following steps: adding 0.4mmol of 1,3, 5-tri (p-formylphenyl) benzene, 1.2mmol of tetraethylenepentamine, 8mL of 1,3, 5-trimethylbenzene and 6mL of 1, 4-dioxane into a polytetrafluoroethylene thick-wall pressure-resistant bottle, sealing by a polytetrafluoroethylene screw plug, and performing ultrasonic dispersion for 20 min; transferring the polytetrafluoroethylene thick-wall pressure-resistant bottle into a microwave reactor, and setting a temperature rise program as follows: the temperature of the microwave reactor is increased from 40 ℃ to 80 ℃ in 0-6 h; the temperature of the microwave reactor is increased from 80 ℃ to 90 ℃ within 6-8h, and is kept at 90 ℃ for 16 h; reducing the temperature of the microwave reactor from 90 ℃ to 60 ℃ within 24h-30 h; the temperature of the microwave reactor is increased from 60 ℃ to 100 ℃ within 30h-36h, and is kept at 100 ℃ for 12 h; the temperature of the microwave reactor is reduced from 100 ℃ to 60 ℃ within 48h to 54 h; the temperature of the microwave reactor is increased from 60 ℃ to 120 ℃ for 54h-60h, and the temperature is kept at 120 ℃ for 12 h; and after the reaction is finished, naturally cooling to room temperature, collecting filter residues by using a vacuum filtration method, leaching the filter residues by using dimethyl sulfoxide, acetone, ethanol and dichloromethane in sequence, and drying in vacuum at 60 ℃ for 12 hours to obtain the spiral COFs with infinite and ordered growth.
As shown in FIG. 1, the transmission electron microscopy images of the COFs with spiral infinite ordered growth prepared by the above steps have an inner diameter of about 400nm and an outer diameter of about 1500nm, and have regular shapes and uniform spiral ring spacing.
The prepared spiral COFs material for infinite and ordered growth is used for separating and purifying the residue of quinolone drugs (including but not limited to enrofloxacin, ciprofloxacin, ofloxacin, pefloxacin, norfloxacin, lomefloxacin, flumequine, oxolinic acid, marbofloxacin, sarafloxacin, danofloxacin, difloxacin, fleroxacin, cinoxacin, enoxacin, nalidixic acid and orbifloxacin) in food: weighing 2.0g of homogenized cucumber sample, adding 30mg of spiral infinite ordered growth COFs material and 10mL of acetonitrile into a 50mL centrifuge tube, carrying out vortex 20min and 12000r/min centrifugation for 8min, and analyzing supernate by using an ultra-fast liquid chromatography-tandem mass spectrometer (UFLC-MS/MS), namely completing the application of spiral infinite ordered growth COFs in purifying quinolone drug residues in cucumbers.
As shown in fig. 2, the LC-MS/MS spectrum of the residue of quinolone drugs in the purified cucumber spiked sample is shown.
The standard recovery rate and precision of the cucumber sample purified by adopting the spiral COFs material with infinite and ordered growth are shown in the following table,
table 1 linear equation of residue of quinolone derivatives, recovery, precision, limit of quantitation and limit of detection (n ═ 9)
aThe standard addition concentration of enrofloxacin, ofloxacin, lomefloxacin, flumequine, oxolinic acid, marbofloxacin, danofloxacin, difloxacin, fleroxacin, cinoxacin, enoxacin, nalidixic acid and orbifloxacin is as follows: 0.4ug/kg, 4.0ug/kg, 16.0 ug/kg; the standard concentration of ciprofloxacin, pefloxacin, norfloxacin and sarafloxacin is 4.0ug/kg, 40ug/kg and 160 ug/kg;bthe precision in the day;cprecision of day
After the helical COFs material growing in an infinite and ordered way is adopted to separate and purify the residue of the quinolone drugs in a cucumber sample, the influence of the matrix inhibition effect on qualitative and quantitative analysis of the quinolone drugs is obviously improved, and the standard addition recovery rate is 76.9-118%.
In some embodiments, a method for preparing helical infinite ordered growth COFs materials comprises the following steps: the method comprises the following steps: adding 0.4mmol of 1,3, 5-tri (p-formylphenyl) benzene, 1.2mmol of tetraethylenepentamine, 8mL of 1,3, 5-trimethylbenzene and 6mL of 1, 4-dioxane into a polytetrafluoroethylene thick-wall pressure-resistant bottle, sealing by a polytetrafluoroethylene screw plug, and performing ultrasonic dispersion for 20 min; transferring the polytetrafluoroethylene thick-wall pressure-resistant bottle into a microwave reactor, and setting a temperature rise program as follows: the temperature of the microwave reactor is increased from 40 ℃ to 80 ℃ in 0-6 h; the temperature of the microwave reactor is increased from 80 ℃ to 90 ℃ within 6-8h, and is kept at 90 ℃ for 4 h; the temperature of the microwave reactor is reduced from 90 ℃ to 60 ℃ within 12h to 18 h; the temperature of the microwave reactor is increased from 60 ℃ to 100 ℃ within 18h-24h, and is kept at 100 ℃ for 12 h; the temperature of the microwave reactor is reduced from 100 ℃ to 60 ℃ within 36h-42 h; the temperature of the microwave reactor is increased from 60 ℃ to 120 ℃ for 42h to 48h, and the temperature is kept at 120 ℃ for 12 h; and after the reaction is finished, naturally cooling to room temperature, collecting filter residues by using a vacuum filtration method, leaching the filter residues by using dimethyl sulfoxide, acetone, ethanol and dichloromethane in sequence, and drying in vacuum at 60 ℃ for 12 hours to obtain the spiral COFs with infinite and ordered growth.
In some embodiments, a method for preparing helical infinite ordered growth COFs materials comprises the following steps: the method comprises the following steps: adding 0.6mmol of 4- (4-formylphenoxy) benzaldehyde, 1.4mmol of tetraethylenepentamine, 8mL of 1,3, 5-trimethylbenzene and 6mL of 1, 4-dioxane into a polytetrafluoroethylene thick-wall pressure-resistant bottle, sealing with a polytetrafluoroethylene spiral plug, and ultrasonically dispersing for 20 min; transferring the polytetrafluoroethylene thick-wall pressure-resistant bottle into a microwave reactor, and setting a temperature rise program as follows: the temperature of the microwave reactor is increased from 40 ℃ to 80 ℃ in 0-6 h; the temperature of the microwave reactor is increased from 80 ℃ to 90 ℃ within 6-8h, and is kept at 90 ℃ for 4 h; the temperature of the microwave reactor is reduced from 90 ℃ to 60 ℃ within 12h to 18 h; the temperature of the microwave reactor is increased from 60 ℃ to 100 ℃ within 18h-24h, and is kept at 100 ℃ for 12 h; the temperature of the microwave reactor is reduced from 100 ℃ to 60 ℃ within 36h-42 h; the temperature of the microwave reactor is increased from 60 ℃ to 120 ℃ for 42h to 48h, and the temperature is kept at 120 ℃ for 24 h; and after the reaction is finished, naturally cooling to room temperature, collecting filter residues by using a vacuum filtration method, leaching the filter residues by using dimethyl sulfoxide, acetone, ethanol and dichloromethane in sequence, and drying in vacuum at 60 ℃ for 12 hours to obtain the spiral COFs with infinite and ordered growth.
In some embodiments, a method for preparing helical infinite ordered growth COFs materials comprises the following steps: the method comprises the following steps: adding 0.8mmol of 4- (4-formylphenoxy) benzaldehyde, 1.6mmol of tetraethylenepentamine, 8mL of 1,3, 5-trimethylbenzene and 6mL of 1, 4-dioxane into a polytetrafluoroethylene thick-wall pressure-resistant bottle, sealing with a polytetrafluoroethylene spiral plug, and ultrasonically dispersing for 20 min; transferring the polytetrafluoroethylene thick-wall pressure-resistant bottle into a microwave reactor, and setting a temperature rise program as follows: the temperature of the microwave reactor is increased from 40 ℃ to 80 ℃ in 0-6 h; the temperature of the microwave reactor is increased from 80 ℃ to 90 ℃ within 6-8h, and is kept at 90 ℃ for 4 h; the temperature of the microwave reactor is reduced from 90 ℃ to 60 ℃ within 12h to 18 h; the temperature of the microwave reactor is increased from 60 ℃ to 100 ℃ within 18h-24h, and is kept at 100 ℃ for 12 h; the temperature of the microwave reactor is reduced from 100 ℃ to 60 ℃ within 36h-42 h; the temperature of the microwave reactor is increased from 60 ℃ to 120 ℃ for 42h to 48h, and the temperature is kept at 120 ℃ for 24 h; and after the reaction is finished, naturally cooling to room temperature, collecting filter residues by using a vacuum filtration method, leaching the filter residues by using dimethyl sulfoxide, acetone, ethanol and dichloromethane in sequence, and drying in vacuum at 60 ℃ for 12 hours to obtain the spiral COFs with infinite and ordered growth.
In some embodiments, a method for preparing helical infinite ordered growth COFs materials comprises the following steps: the method comprises the following steps: adding 0.2mmol of 1,3, 5-tri (p-formylphenyl) benzene, 0.6mmol of tetraethylenepentamine, 5mL of 1,3, 5-trimethylbenzene and 5mL of 1, 4-dioxane into a polytetrafluoroethylene thick-wall pressure-resistant bottle, sealing by a polytetrafluoroethylene screw plug, and performing ultrasonic dispersion for 20 min; transferring the polytetrafluoroethylene thick-wall pressure-resistant bottle into a microwave reactor, and setting a temperature rise program as follows: the temperature of the microwave reactor is increased from 40 ℃ to 80 ℃ in 0-6 h; the temperature of the microwave reactor is increased from 80 ℃ to 90 ℃ within 6-8h, and is kept at 90 ℃ for 4 h; the temperature of the microwave reactor is reduced from 90 ℃ to 60 ℃ within 12h to 18 h; the temperature of the microwave reactor is increased from 60 ℃ to 100 ℃ within 18h-24h, and is kept at 100 ℃ for 12 h; the temperature of the microwave reactor is reduced from 100 ℃ to 60 ℃ within 36h-42 h; the temperature of the microwave reactor is increased from 60 ℃ to 120 ℃ for 42h to 48h, and the temperature is kept at 120 ℃ for 12 h; and after the reaction is finished, naturally cooling to room temperature, collecting filter residues by using a vacuum filtration method, leaching the filter residues by using dimethyl sulfoxide, acetone, ethanol and dichloromethane in sequence, and drying in vacuum at 60 ℃ for 12 hours to obtain the spiral COFs with infinite and ordered growth.
In some embodiments, a method for preparing helical infinite ordered growth COFs materials comprises the following steps: the method comprises the following steps: adding 0.8mmol of 1,3, 5-tri (p-formylphenyl) benzene, 2.4mmol of tetraethylenepentamine, 10mL of 1,3, 5-trimethylbenzene and 10mL of 1, 4-dioxane into a polytetrafluoroethylene thick-wall pressure-resistant bottle, sealing by a polytetrafluoroethylene screw plug, and performing ultrasonic dispersion for 20 min; transferring the polytetrafluoroethylene thick-wall pressure-resistant bottle into a microwave reactor, and setting a temperature rise program as follows: the temperature of the microwave reactor is increased from 40 ℃ to 80 ℃ in 0-6 h; the temperature of the microwave reactor is increased from 80 ℃ to 90 ℃ within 6-8h, and is kept at 90 ℃ for 16 h; the temperature of the microwave reactor is reduced from 90 ℃ to 60 ℃ within 24h-32 h; the temperature of the microwave reactor is increased from 60 ℃ to 100 ℃ within 32h-38h, and is kept at 100 ℃ for 12 h; the temperature of the microwave reactor is reduced from 100 ℃ to 60 ℃ within 50h-56 h; the temperature of the microwave reactor is increased from 60 ℃ to 120 ℃ for 56-62 h, and the temperature is kept at 120 ℃ for 24 h; and after the reaction is finished, naturally cooling to room temperature, collecting filter residues by using a vacuum filtration method, leaching the filter residues by using dimethyl sulfoxide, acetone, ethanol and dichloromethane in sequence, and drying in vacuum at 60 ℃ for 12 hours to obtain the spiral COFs with infinite and ordered growth.
The application of the spiral infinite ordered growth COFs material comprises the steps of weighing a homogenized food sample in a centrifuge tube, adding a proper amount of the COFs material and acetonitrile, carrying out vortex centrifugation, and analyzing supernate by using an ultrafast liquid chromatography-tandem mass spectrometer.
In some embodiments, in the step of weighing the homogenized food sample in a centrifuge tube and adding the appropriate amount of the COFs material and the acetonitrile, 5 parts by mass of the COFs material and 1.3 parts by mass of the acetonitrile are added for every 2300 parts by mass of the homogenized food sample.
In some embodiments, in the step of weighing the homogenized food sample in a centrifuge tube and adding appropriate amounts of the COFs material and acetonitrile, 8 parts by mass of the COFs material and 2 parts by mass of the acetonitrile are added for every 400 parts by mass of the homogenized food sample.
In some embodiments, in the step of weighing the homogenized food sample in a centrifuge tube and adding appropriate amounts of the COFs material and acetonitrile, 2 parts by mass of the COFs material and 1 part by mass of the acetonitrile are added for every 200 parts by mass of the homogenized food sample.
In some embodiments, in the step of vortex centrifugation, the vortex is performed for 10-30 min and the centrifugation is performed for 5-10 min at a rotation speed of 12000 r/min.
It will be understood that the present application is not limited to the precise arrangements described above and shown in the drawings and that various modifications and changes may be made without departing from the scope thereof. The scope of the application is limited only by the appended claims.
Claims (10)
1. The spiral infinite ordered growth COFs material is characterized in that: the reaction monomers of the COFs material comprise rigid aromatic aldehyde monomers and flexible aliphatic amine monomers.
2. The helical infinite ordered growth COFs material of claim 1, wherein: the rigid aromatic aldehyde monomer is at least one of 4- (4-formylphenoxy) benzaldehyde, 1,3, 5-tri (formylphenyl) benzene and 4,4' -biphenyldicarboxaldehyde.
3. The helical infinite ordered growth COFs material of claim 1, wherein: the flexible aliphatic amine monomer is at least one of diethylenetriamine, triethylene tetramine and tetraethylene pentamine.
4. A method for preparing helical infinite ordered growth COFs materials as claimed in any one of claims 1 to 3, comprising the steps of:
adding a reaction monomer of the COFs material into a polytetrafluoroethylene pressure-resistant bottle, and dispersing the reaction monomer for 10-30 min by using ultrasonic waves;
transferring the polytetrafluoroethylene pressure-resistant bottle into a microwave reactor, and controlling the heating reaction process and the circulating heating reaction times by adopting a microwave program heating method;
and after the heating reaction is finished, naturally cooling to room temperature, collecting filter residues by using a vacuum filtration method, leaching the filter residues by using dimethyl sulfoxide, acetone, ethanol and dichloromethane in sequence, and drying to obtain the spiral infinite ordered growth C OFs.
5. The method for preparing helical infinite ordered growth COFs materials according to claim 4, wherein: in the step of adding the reaction monomer of the COFs material into the polytetrafluoroethylene pressure-resistant bottle, 0.2-0.8 mmol of 1,3, 5-tri (p-formylphenyl) benzene, 0.6-2.4 mmol of tetraethylenepentamine, 5-10 mL of 1,3, 5-trimethylbenzene and 5-10 mL of 1, 4-dioxane are selected and added into the polytetrafluoroethylene thick-wall pressure-resistant bottle.
6. The method for preparing COFs materials according to claim 4, wherein the step of controlling the heating reaction process and the number of heating reactions in a cyclic manner by using a microwave programmed heating method comprises the following steps:
the first stage is 6h, the temperature of the microwave reactor is increased from 40 ℃ to 80 ℃;
in the second stage for 2 hours, the temperature of the microwave reactor is increased from 80 ℃ to 90 ℃, and the microwave reactor is kept at 90 ℃ for 4-16 hours;
in the third stage of 6h, the temperature of the microwave reactor is reduced from 90 ℃ to 60 ℃;
in the fourth stage, the temperature of the microwave reactor is increased from 60 ℃ to 100 ℃ and is kept at 100 ℃ for 4-16 h;
in the fifth stage for 6h, the temperature of the microwave reactor is reduced from 100 ℃ to 60 ℃;
in the sixth stage 6h, the temperature of the microwave reactor is increased from 60 ℃ to 120 ℃, and the temperature is kept at 120 ℃ for 12-24 h.
7. The method for preparing the COFs materials capable of infinitely and orderly growing in the spiral shape according to claim 4, wherein the drying step comprises the step of drying the washed filter residue for 6-12 hours in a vacuum environment at 40-80 ℃.
8. Use of the helical infinitely ordered growth COF s materials according to claim 4, wherein: weighing a homogenized food sample in a centrifuge tube, adding a proper amount of the COFs material and acetonitrile, carrying out vortex centrifugation, and analyzing the supernatant by using an ultrafast liquid chromatography-tandem mass spectrometer.
9. The use of the COFs materials according to claim 8, wherein in the step of weighing the homogenized food sample in a centrifuge tube and adding an appropriate amount of the COFs materials and acetonitrile, 2-8 parts by mass of the COFs materials and 1-2 parts by mass of acetonitrile are added to 200-400 parts by mass of the homogenized food sample.
10. The use of the helical infinite order growth C OFs material according to claim 8, wherein in the step of vortex centrifugation, the vortex is performed for 10-30 min, and the vortex is performed for 5-10 min at a rotation speed of 12000 r/min.
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