CN115260516B - Preparation method and application of fluorescent probe material based on sulfonyl calixarene structure - Google Patents

Preparation method and application of fluorescent probe material based on sulfonyl calixarene structure Download PDF

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CN115260516B
CN115260516B CN202210985089.6A CN202210985089A CN115260516B CN 115260516 B CN115260516 B CN 115260516B CN 202210985089 A CN202210985089 A CN 202210985089A CN 115260516 B CN115260516 B CN 115260516B
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sulfonyl
fluorescent probe
probe material
material based
calixarene
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CN115260516A (en
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单威龙
侯欢欢
王彩霞
李霞
周可祥
熊金华
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Anhui University of Technology AHUT
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    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008—Supramolecular polymers
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N2021/6432—Quenching

Abstract

The invention discloses a preparation method and application of a fluorescent probe material based on a sulfonyl calixarene structure, which comprises the steps of taking cheap p-tert-butyl phenol and elemental sulfur as raw materials, synthesizing through two-step reaction to obtain p-tert-butyl sulfonyl calixarene, and obtaining a novel metal-organic coordination polymer fluorescent probe with the sulfonyl calixarene structure through coordination assembly with 4,4' -biphenyldicarboxylic acid and zinc nitrate. Compared with the prior art, the fluorescent probe material has the advantages of simple preparation method, easily obtained raw materials, mild reaction conditions, high yield, high sensitivity and the like. Meanwhile, the prepared metal-organic coordination polymer with the sulfonyl calixarene structure is insoluble in water, strong acid, strong base and general organic reagents, has good structural stability and good fluorescence property, and can selectively identify aromatic nitro explosive hazards. Can be used as fluorescent probes of nitrobenzene, 2-nitrophenol, 3-nitrophenol, 4-nitrophenol, 3-nitrotoluene, 4-nitrotoluene and the like.

Description

Preparation method and application of fluorescent probe material based on sulfonyl calixarene structure
Technical Field
The invention belongs to the field of preparation and application of calixarene coordination polymers, and particularly relates to a preparation method and application of a fluorescent probe material based on a sulfonyl calixarene structure.
Background
The aromatic nitro compound refers to a compound with one or more nitro substituents on an aromatic ring, and is a substance with toxicity, mutagenesis and carcinogenesis, and the polynitro aromatic compound (such as trinitrotoluene) also has strong explosiveness and low safety performance. The aromatic nitro compound is also an important chemical raw material and intermediate in fine chemical industry such as medicine, pesticide, synthetic dye and the like, and inevitably contains a certain amount of aromatic nitro compound in wastewater generated in the production and use processes of the aromatic nitro compound, thereby causing great threat to the safety of water body environment. Therefore, the method has important practical significance for rapidly and sensitively detecting the aromatic nitro compound.
Currently, detection methods that have been developed include fluorescence, electrochemical sensor, chemical field test, chemical resistance, portable mass spectrometry, gas chromatography-mass spectrometry (GC-MS), surface Enhanced Raman Spectroscopy (SERS), ion mobility spectrometry, and X-ray methods, among others. However, most detection methods have high cost and complicated detection process, and the application of the detection methods in practical detection is severely limited by the factors. For example, a chemical field test method has strong detection specificity but low sensitivity, and cannot realize remote detection; the X-ray method can detect a large number of hidden explosive devices, and the portable mass spectrometry can accurately identify the chemical structure of the explosive, but the practicability in a complex environment is reduced due to the intensive hardware characteristic of the devices; although the gas chromatography-mass spectrometry (GC-MS) method, the Surface Enhanced Raman Spectroscopy (SERS) method and the like can accurately detect explosives, the method has the defects of expensive instruments, complex operation, inconvenience in carrying and the like. Therefore, it is of great significance to develop a detection method having the advantages of low cost, simple operation, high sensitivity, and the like. In recent years, fluorescent probe technology has proven to be one of the effective means for detecting toxic explosives such as nitro compounds. The method has low technical requirements, low cost, strong practicability and high detection sensitivity, so that the method has a strong recognition effect on a plurality of nitro explosive molecules and even certain specific functional groups.
Supramolecular recognition has been a focus of research in the field of supramolecular chemistry. Calixarenes are particularly favored by scientists as third generation host supramolecular compounds following crown ethers, cyclodextrins due to their unique structure and superior performance. They are a class of cup-shaped oligomeric macrocyclic compounds, usually the middle part is composed of benzene ring, the lower end is connected with phenolic hydroxyl, and they have controllable hydrophobic cavity, and are ideal host compounds for wrapping guest molecules. In addition, the macrocyclic compound also has the characteristics of flexible and changeable structure, easy functional modification, good coordination capacity and the like. For example, by introducing different groups of functional calixarenes into the upper edge of the calixarene, a host compound with lipophilicity, hydrophilicity and ionophore, which takes a cup ring as a framework, can be formed, so that guest molecules with different properties can be identified. And phenolic hydroxyl in the calixarene structural unit and heteroatoms modified by bridging methylene are good metal coordination sites, and are easy to form a conical structural unit after being coordinated with metal ions, and the structural unit can be further assembled to obtain the metal organic supermolecular compound with novel structure and excellent performance.
At present, no preparation method and application of a p-tert-butylsulfonyl calixarene-based metal-organic coordination polymer fluorescent probe material exist in the prior art.
Disclosure of Invention
The invention aims to provide a preparation method and application of a fluorescent probe material based on a sulfonyl calixarene structure, wherein the fluorescent probe is obtained by coordination assembly of p-tert-butyl sulfonyl calixarene, 4' -biphenyl dicarboxylic acid and zinc nitrate; the fluorescent probe can be used for detecting specific aromatic nitro compounds, and has great industrial application value and popularization prospect.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of a fluorescent probe material based on a sulfonyl calixarene structure comprises the following steps:
A. taking p-tert-butylphenol, elemental sulfur and NaOH as raw materials, adding tetraethylene glycol dimethyl ether (TEGDME), slowly heating to 165 ℃ in an inert atmosphere, reacting for 2 hours, then slowly heating to 230 ℃, continuing to react for 4 hours, cooling to 100 ℃, adding toluene and sulfuric acid, cooling, extracting, adding methanol into a toluene layer, separating out solids, filtering to obtain white solids, and drying;
B. adding NaBO to the product prepared in step A as a reactant 3 Heating trichloromethane and glacial acetic acid to 50 ℃, reacting for 18 hours, adding distilled water into the reaction mixture after the reaction is finished, continuing stirring for 1 hour, extracting by using trichloromethane, and adding anhydrous Na 2 SO 4 Drying, filtering, and concentrating the filtrate with rotary evaporatorAdding methanol until solid is separated out, filtering to obtain white solid, and drying;
C. and D, putting the product prepared in the step B and 4,4 '-biphenyldicarboxylic acid into a glass bottle, adding N, N' -Dimethylacetamide (DMA), dissolving, adding zinc nitrate hexahydrate and deionized water, putting into an oven for reaction for a period of time, slowly cooling to room temperature, separating out light yellow single crystals, washing with methanol and diethyl ether, and drying to obtain the coordination polymer fluorescent probe material.
Preferably, in step a, the inert atmosphere is nitrogen or argon.
Preferably, in step a, the mass ratio of p-tert-butylphenol, elemental sulfur and NaOH employed is 2;
preferably, in step a, the volume ratio of toluene to sulfuric acid employed is 1.
Preferably, in the step A, the concentrated sulfuric acid concentration is 6mol/L.
Preferably, in step B, the product prepared in step A and NaBO 3 The mass ratio of the mixed reactants of (1).
Preferably, in step B, the volume ratio of chloroform to glacial acetic acid used is 3.
Preferably, in the step B, vacuum concentration treatment is adopted when the filtrate is concentrated, and the vacuum concentration treatment condition is that the temperature is not higher than 40 ℃ and the vacuum degree is 0.09-0.1MPa.
Preferably, in step C, a volume ratio of N, N' -dimethylacetamide to deionized water of 1.
Preferably, in step C, the mass ratio of the product prepared in step B, 4' -biphenyldicarboxylic acid and zinc nitrate hexahydrate is 1.
Preferably, in step C, the temperature of the solvothermal is 100 to 140 ℃ and the reaction time is 12 to 16 hours, more preferably, the temperature of the solvothermal is 120 ℃ and the reaction time is 12 hours.
The prepared fluorescent probe material is a metal-organic coordination polymer based on a sulfonyl calixarene structure, is insoluble in water and common organic reagents, has good structural stability and obvious fluorescence intensity, can perform fluorescence identification on aromatic nitro compounds, and is applied to detecting whether the aromatic nitro explosive dangerous goods are contained in water or the organic reagents.
The invention has the beneficial effects that:
1. the metal-organic coordination polymer based on the sulfonyl calixarene structure has a novel structure and a hydrophobic cavity, can selectively identify aromatic nitro explosive hazards such as Nitrobenzene (NB), 2-nitrophenol (2-NP), 3-nitrophenol (3-NP), 4-nitrophenol (4-NP), 3-nitrotoluene (3-NT) and 4-nitrotoluene (4-NT), and has a potential application prospect in the detection of nitro explosives due to the fact that the fluorescence intensity can be greatly changed after identification.
2. The preparation method is simple, the raw materials are easy to obtain, the reaction conditions are mild, the yield is high, and the sensitivity is high.
Drawings
FIG. 1 is an X-ray powder diffraction (XRD) pattern under different conditions of the metal-organic coordination polymer based on sulfonyl calixarene structure prepared in example 3;
FIG. 2 is an infrared spectrum of a sulfonyl calixarene structure-based metal-organic coordination polymer prepared in example 3;
FIG. 3 is a diagram of asymmetric structural units of a sulfonyl calixarene structure-based metal-organic coordination polymer single crystal prepared in example 3;
FIG. 4 is a two-dimensional and three-dimensional structural diagrams of a sulfonyl calixarene structure-based metal-organic coordination polymer single crystal prepared in example 3;
FIG. 5 is a solid fluorescence excitation spectrum of ligand 4,4' -biphenyldicarboxylic acid and the sulfonyl calixarene structure-based metal-organic coordination polymer prepared in example 3 at a wavelength of 300 nm;
FIG. 6 is a graph showing fluorescence measurements of the metal-organic coordination polymer based on a sulfonyl calixarene structure prepared in example 3 in the presence of Nitrobenzene (NB), 2-nitrophenol (2-NP), 3-nitrophenol (3-NP), 4-nitrophenol (4-NP), 3-nitrotoluene (3-NT), and 4-nitrotoluene (4-NT), respectively;
FIG. 7 is a graph showing fluorescence measurements of the metal-organic coordination polymer prepared in example 3 on NB and linear fitting quenching constants (0.95X 10) with increasing concentrations of Nitrobenzene (NB) 3 M -1 ) A drawing;
FIG. 8 is a graph showing fluorescence test pattern and linear fitting quenching constant (1.54X 10) of the metal-organic coordination polymer prepared in example 3 for 2-NP with increasing concentration of 2-nitrophenol (2-NP) 4 M -1 ) A drawing;
FIG. 9 is a graph showing fluorescence test pattern and linear fitting quenching constant (1.56X 10) of the metal-organic coordination polymer prepared in example 3 for 3-NP with increasing concentration of 3-nitrophenol (3-NP) 4 M -1 ) A drawing;
FIG. 10 is a graph showing fluorescence test pattern and linear fitting quenching constant (4.31X 10) of the metal-organic coordination polymer prepared in example 3 for 4-NP with increasing concentration of 4-nitrophenol (4-NP) 4 M -1 ) A drawing;
FIG. 11 is a graph showing fluorescence test and linearly fitted quenching constant (1.41X 10) of 3-NT versus metal-organic complex polymer prepared in example 3 with increasing concentration of 3-nitrotoluene (3-NT) 3 M -1 ) A drawing;
FIG. 12 is a graph showing fluorescence measurements and linearly fitted quenching constants (4.72X 10) of the metal-organic coordination polymer prepared in example 3 for 4-NT with an increase in the concentration of 4-nitrotoluene (4-NT) 3 M -1 ) Figure (a).
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation method of the p-tert-butylthiacalixarene comprises the following steps:
p-tert-butylphenol (30g, 0.2mol), elemental sulfur (13g, 0.4mol) and NaOH (4g, 0.1mol) were put into a 100mL eggplant-shaped bottle, and 11mL of tetraethyleneglycol dimethyl ether (TEGDME) was added thereto under an inert atmosphere. The temperature was slowly raised to 165 ℃ for 2 hours, and then slowly raised to 230 ℃ for further 4 hours. When the temperature was lowered to 100 ℃, 40mL of toluene and 40mL of sulfuric acid (6 mol/L) were slowly added thereto, and after cooling to room temperature, extraction was carried out to obtain a toluene layer. The resulting mixture was transferred to a 1000mL beaker, 500mL of methanol was added, stirred for 10min, filtered, and the filter cake was washed three times with methanol to give a white powder.
Example 2
The preparation method of the p-tert-butyl sulfonyl calixarene comprises the following steps:
the product prepared in example 1 (2g, 2.76mmol) and NaBO 3 (4 g,2.6 mmol) was placed in a 250mL two-necked flask, and 60mL of chloroform and 100mL of glacial acetic acid were added thereto, and the temperature was raised to 50 ℃ to react for 18 hours. After the reaction, the reaction mixture was placed in a 500mL beaker, 150mL of water was added and stirred for 1 hour, and then 120mL of chloroform was added and extracted 3 times with 40mL of chloroform each time to obtain a chloroform layer. With anhydrous Na 2 SO 4 Drying, filtering, concentrating, adding 200mL of methanol, filtering and washing to obtain white powder.
Example 3
A preparation method of a metal-organic coordination polymer with a sulfonyl calixarene structure comprises the following steps:
the product prepared in example 2 (8.5mg, 0.01mmol) and 4,4 '-biphenyldicarboxylic acid (2.4mg, 0.01mmol) were placed in a 10mL glass bottle, 0.5mLN was added, and after N' -Dimethylacetamide (DMA) was dissolved, zinc nitrate hexahydrate (8.9mg, 0.03mmol) was added, followed by 0.5mL of deionized water. Putting the mixture into a 120 ℃ oven to react for 12 hours, taking out the mixture, slowly cooling the mixture to room temperature to separate out yellow single crystals, and washing the yellow single crystals with methanol and ether for not less than three times respectively. Drying treatment gives yellow crystals. Yield: 92 percent. FT-IR (KBrdisk, cm) -1 ):v＝3546(w),3446(m),2962(s),1606(s),1541(w),1494(m),1462(w),1402(w),1385(m),1340(w),1290(w),1265(m),1222(w),1196(w),1179(w),1157(w),1132(m),1082(s),1021(w),905(w),839(w),797(s),774(m),682(w),625(m),560(s),526(w),480(w),435 (w) (as shown in FIG. 2)
The structure and each spectrum of the metal-organic coordination polymer based on sulfonyl calixarene structure prepared in example 3 are shown in fig. 1 to 5.
Example 4
Fluorescence recognition experiments of sulfonyl calixarene structure-based metal-organic coordination polymers from example 3 on six aromatic nitro compounds:
the aromatic nitro compounds involved in the fluorescent recognition are Nitrobenzene (NB), 2-nitrophenol (2-NP), 3-nitrophenol (3-NP), 4-nitrophenol (4-NP), 3-nitrotoluene (3-NT) and 4-nitrotoluene (4-NT).
The concentration of the compound of the present invention is 5X 10 -4 mol/L, concentration of all aromatic nitro compounds is 2X 10 -2 mol/L. The specific method comprises the following steps: 2mL of 5X 10 solution were added to several tubes -4 The methanol solution of the compound of the present invention was added to each of these test tubes to a concentration of 2X 10 by adding methanol solutions of Nitrobenzene (NB), 2-nitrophenol (2-NP), 3-nitrophenol (3-NP), 4-nitrophenol (4-NP), 3-nitrotoluene (3-NT) and 4-nitrotoluene (4-NT) to the test tubes, respectively -2 mol/L, ultrasonic testing for 30min at room temperature, and then performing fluorescence test to obtain an excitation curve as shown in figure 6, wherein as is obvious from figure 6, when the compound of the invention is not added with any aromatic nitro compound, the strongest excitation peak exists at 416 nm. When the aromatic nitro compound is added, the strongest excitation peak of the compound of the present invention changes. It is clear that Nitrobenzene (NB), 2-nitrophenol (2-NP), 3-nitrophenol (3-NP), 4-nitrophenol (4-NP), 3-nitrotoluene (3-NT) and 4-nitrotoluene (4-NT) can attenuate this most intense excitation peak to near quenching.
Example 5
Fluorescence quenching experiments for p-Nitrophenyl (NB) metal-organic coordination polymers based on sulfonyl calixarene structures from example 3:
the concentration of the compound of the present invention was fixed at 5X 10 -4 mol/L, the NB concentration was gradually increased, and 1 drop was gradually increased to 20 drops. The specific method comprises the following steps: 2mL of 5X 10 solution were added to the cuvette -4 mol/L of a solution of a compound of the invention in methanol, cellPerforming ultrasonic treatment at the temperature for 30min, dropwise adding 1-20 drops of NB methanol solution into the cuvette, and performing fluorescence test respectively to obtain an excitation curve as shown in FIG. 7, wherein the maximum relative intensity is the excitation peak of the compound of the invention. As can be seen from FIG. 7, the fluorescence intensity of the compounds of the present invention gradually decreased with increasing NB concentration, and eventually was nearly quenched.
Example 6
Fluorescence quenching experiments for 2-nitrophenol (2-NP) with metal-organic coordination polymers based on sulfonyl calixarene structures from example 3:
the concentration of the compound of the present invention was fixed at 5X 10 -4 mol/L, gradually increasing the concentration of 2-NP, and gradually increasing 1 drop to 20 drops. The specific method comprises the following steps: 2mL of 5X 10 solution were added to the cuvette -4 And (3) performing ultrasonic treatment on a mol/L methanol solution of the compound of the invention for 30min at room temperature, dropwise adding 1-20 drops of the methanol solution of 2-NP into the cuvette, and performing fluorescence test respectively to obtain an excitation curve as shown in figure 8, wherein the maximum relative intensity is an excitation peak of the compound of the invention. As can be seen from FIG. 8, the fluorescence intensity of the compound of the present invention gradually decreased with increasing concentration of 2-NP, and finally was almost quenched.
Example 7
Fluorescence quenching experiments for 3-nitrophenol (3-NP) with metal-organic coordination polymers based on sulfonyl calixarene structures from example 3:
the concentration of the compound of the present invention was fixed at 5X 10 -4 mol/L, gradually increasing the concentration of 3-NP, and gradually increasing 1 drop to 20 drops. The method comprises the following steps: 2mL of 5X 10 solution were added to the cuvette -4 And (3) performing ultrasonic treatment on a mol/L methanol solution of the compound of the invention for 30min at room temperature, dropwise adding 1-20 drops of the 3-NP methanol solution into the cuvette, and performing fluorescence test respectively to obtain an excitation curve as shown in figure 9, wherein the maximum relative intensity is an excitation peak of the compound of the invention. As can be seen from FIG. 9, the fluorescence intensity of the compound of the present invention gradually decreased with increasing concentration of 3-NP, and finally was almost quenched.
Example 8
Fluorescence quenching experiment of sulfonyl calixarene structure-based metal-organic coordination polymers on 4-nitrophenol (4-NP) from example 3:
the concentration of the compound of the present invention was fixed at 5X 10 -4 mol/L, gradually increasing the concentration of 4-NP, and gradually increasing 1 drop to 20 drops. The specific method comprises the following steps: 2mL of 5X 10 solution were added to the cuvette -4 And (3) performing ultrasonic treatment on mol/L methanol solution of the compound of the invention for 30min at room temperature, dropwise adding 1-20 drops of methanol solution of 4-NP into the cuvette, and performing fluorescence test respectively to obtain an excitation curve as shown in figure 10, wherein the maximum relative intensity is an excitation peak of the compound of the invention. As can be seen from FIG. 10, the fluorescence intensity of the compound of the present invention gradually decreased with increasing concentration of 4-NP, and finally was almost quenched.
Example 9
Fluorescence quenching experiment of sulfonyl calixarene structure-based metal-organic coordination polymers from example 3 on 3-nitrotoluene (3-NT):
the concentration of the compound of the present invention was fixed at 5X 10 -4 mol/L, gradually increasing the concentration of 3-NT, and gradually increasing 1 drop to 20 drops. The specific method comprises the following steps: 2mL of 5X 10 solution were added to the cuvette -4 And (3) performing ultrasonic treatment on mol/L methanol solution of the compound of the invention for 30min at room temperature, dropwise adding 1-20 drops of 3-NT methanol solution into the cuvette, and performing fluorescence test respectively to obtain an excitation curve as shown in FIG. 11, wherein the maximum relative intensity is an excitation peak of the compound of the invention. As can be seen from FIG. 11, the fluorescence intensity of the compound of the present invention gradually decreased with increasing concentration of 3-NT, and finally was almost quenched.
Example 10
Fluorescence quenching experiment of 4-nitrotoluene (4-NT) with metal-organic coordination polymer based on sulfonyl calixarene structure from example 3:
the concentration of the compound of the present invention was fixed at 5X 10 -4 mol/L, gradually increasing the concentration of 4-NT, and gradually increasing 1 drop to 20 drops. The specific method comprises the following steps: 2mL of 5X 10 solution were added to the cuvette -4 Performing ultrasonic treatment on mol/L methanol solution of the compound of the invention at room temperature for 30min, then dropwise adding 1-20 drops of 4-NT methanol solution into the cuvette,fluorescence measurements were performed separately, and the resulting excitation curves are shown in FIG. 12, in which the maximum relative intensity is the excitation peak of the compound of the present invention. As can be seen from FIG. 12, the fluorescence intensity of the compound of the present invention gradually decreased with the gradual increase in the concentration of 4-NT, and finally was almost quenched.
In summary, in the preparation method of the metal-organic coordination polymer based on the structure of the sulfonyl calixarene according to the above embodiment, p-tert-butylphenol, elemental sulfur and NaOH are used as raw materials, a two-step reaction is performed to obtain p-tert-butyl sulfonyl calixarene, 4' -biphenyldicarboxylic acid and zinc nitrate are added for coordination, and finally the metal-organic coordination polymer is obtained. The preparation method is simple, the raw materials are easy to obtain, the reaction conditions are mild, the yield is high, and the repeatability is good. The metal-organic coordination polymer based on the sulfonyl calixarene structure is insoluble in water and common organic reagents, has good structural stability and obvious fluorescence intensity, can identify aromatic nitro explosive hazards, such as Nitrobenzene (NB), 2-nitrophenol (2-NP), 3-nitrophenol (3-NP), 4-nitrophenol (4-NP), 3-nitrotoluene (3-NT) and 4-nitrotoluene (4-NT), has great change in fluorescence after identification, and has potential application prospect in the detection aspect of nitro explosives.
The above detailed description section specifically describes the analysis method according to the present invention. It should be noted that the above description is only for the purpose of helping those skilled in the art better understand the method and idea of the present invention, and not for the limitation of the related contents. The present invention can be appropriately adjusted or modified by those skilled in the art without departing from the principle of the present invention, and the adjustment and modification should also fall within the protection scope of the present invention.

Claims (10)

1. The preparation method of the fluorescent probe material based on the sulfonyl calixarene structure is characterized by comprising the following steps of:
A. taking p-tert-butylphenol, elemental sulfur and NaOH as raw materials, adding tetraethylene glycol dimethyl ether, slowly heating to 165 ℃ in an inert atmosphere, reacting for 2 hours, then slowly heating to 230 ℃, continuing to react for 4 hours, cooling to 100 ℃, adding toluene and sulfuric acid, cooling, extracting, adding methanol into a toluene layer, separating out solids, filtering to obtain white solids, and drying;
B. taking the product prepared in the step A as a reactant, adding NaBO3, trichloromethane and glacial acetic acid, heating to 50 ℃, reacting for 18 hours, after the reaction is finished, adding distilled water into the reaction mixture, continuing stirring for 1 hour, extracting by using trichloromethane, drying by using anhydrous Na2SO4, filtering, concentrating the filtrate by using a rotary evaporator until solid is separated out, adding methanol, filtering to obtain white solid, and drying;
C. and D, putting the product prepared in the step B and 4,4 '-biphenyldicarboxylic acid into a glass bottle, adding N, N' -dimethylacetamide, dissolving, adding zinc nitrate hexahydrate and deionized water, putting into an oven for reaction for a period of time, slowly cooling to room temperature, separating out light yellow single crystals, washing with methanol and diethyl ether, and drying to obtain the coordination polymer fluorescent probe material.
2. The method for preparing a fluorescent probe material based on a sulfonyl calixarene structure according to claim 1, wherein in the step a, the inert atmosphere is nitrogen or argon.
3. The method for preparing a fluorescent probe material based on a sulfonyl calixarene structure according to claim 1, wherein in the step A, the ratio of the amounts of p-tert-butylphenol, elemental sulfur and NaOH is 2.
4. The method for preparing the fluorescent probe material based on the sulfonyl calixarene structure according to claim 1, wherein in the step A, the volume ratio of toluene to sulfuric acid is 1; the concentration of the sulfuric acid is 6mol/L.
5. The method for preparing the fluorescent probe material based on the sulfonyl calixarene structure according to claim 1, wherein in the step B, the mass ratio of the product prepared in the step A to NaBO3 is 1; the volume ratio of the trichloromethane to the glacial acetic acid is 3.
6. The method for preparing a fluorescent probe material based on a sulfonyl calixarene structure according to claim 1, wherein in the step B, vacuum concentration is adopted when the filtrate is concentrated, and the vacuum concentration is performed under the conditions that the temperature is not higher than 40 ℃ and the vacuum degree is 0.09-0.1MPa.
7. The method for preparing the fluorescent probe material based on the sulfonyl calixarene structure according to claim 1, wherein in the step C, the volume ratio of the N, N' -dimethylacetamide to the deionized water is 1.
8. The method for preparing a fluorescent probe material based on a sulfonyl calixarene structure according to claim 1, wherein in step C, the ratio of the amounts of the product prepared in step B, 4' -biphenyldicarboxylic acid and zinc nitrate hexahydrate is 1.
9. The method for preparing a fluorescent probe material based on a sulfonyl calixarene structure according to claim 1, wherein in the step C, the reaction temperature is 100-140 ℃ and the reaction time is 12-16 hours.
10. The application of the fluorescent probe material prepared by the method according to claim 1 in the field of nitro explosive detection.
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