阅读说明：本技术 一种杯芳烃-罗丹明超分子共组装体及其制备方法和应用 (Calixarene-rhodamine supramolecular assembly and preparation method and application thereof ) 是由 肖昕 岑然 张威 刘明 冯贤豪 王成会 陈丽霞 于 2021-06-15 设计创作，主要内容包括：本发明公开了一种杯芳烃-罗丹明超分子共组装体及其制备方法和应用,其分子式为C-(112)H-(103)O-(51)N-2S-(12),可作为荧光探针检测水溶液中Fe～(3+)和Pb～(2+)。本发明的超分子共组装体可作为水溶液中铁离子和钯离子的荧光检测试剂,具有检测快速有效、选择性好、敏感度高、检测成本小和对设备要求低的优点。(The invention discloses a calixarene-rhodamine supramolecular assembly and a preparation method and application thereof, wherein the molecular formula of the calixarene-rhodamine supramolecular assembly is C 112 H 103 O 51 N 2 S 12 Can be used as a fluorescent probe for detecting Fe in aqueous solution 3+ And Pb 2+ . The supermolecule co-assembly can be used as a fluorescent detection reagent for iron ions and palladium ions in an aqueous solution, and has the advantages of quick and effective detection, good selectivity, high sensitivity, low detection cost and low requirement on equipment.)

1. The calixarene-rhodamine supramolecular assembly is characterized in that the molecular formula is C₁₁₂H₁₀₃O₅₁N₂S₁₂The chemical structural formula is as follows:

wherein

2. A method for preparing the calixarene-rhodamine supramolecular assembly of claim 1, comprising: is prepared by co-assembling rhodamine and 4-sulfonyl calix [4] arene as raw materials.

3. The method for preparing calixarene-rhodamine supramolecular assemblies according to claim 2, wherein the method comprises the following steps:

1) mixing rhodamine and 4-sulfonyl calix [4] arene hydrate, adding the mixture into a hydrochloric acid solution, and stirring to dissolve the mixture to obtain a solution A;

2) adding the solution A into an autoclave, carrying out constant-temperature reaction under a heating condition, cooling to room temperature, and standing for crystallization to obtain a crystal B;

3) filtering out the crystal B in the step 2), wherein the crystal B is the calixarene-rhodamine supermolecular assembly.

4. The method of preparing calixarene-rhodamine supramolecular assemblies according to claim 2 or 3, characterized in that: the ratio of the amounts of the rhodamine and the 4-sulfonyl calix [4] arene is less than 1: 3.

5. the method of preparing calixarene-rhodamine supramolecular assemblies according to claim 4, wherein: the ratio of the amounts of rhodamine and 4-sulfonyl calix [4] arene species is equal to 1: 3.

6. the method of preparing calixarene-rhodamine supramolecular assemblies according to claim 3, wherein: the concentration of the hydrochloric acid solution in the step 1) is 6 mol/L.

7. The method of preparing calixarene-rhodamine supramolecular assemblies according to claim 3, wherein: the final temperature of the heating in the step 2) is 95-105 ℃, and the constant temperature time is 0.5-1.5 h; the standing time is 1-3 d.

8. The method of preparing calixarene-rhodamine supramolecular assemblies according to claim 3, wherein: the molecular weight of the crystal B is 2713.17.

9. The calixarene-rhodamine supramolecular assembly as claimed in claim 1 as a fluorescent probe for detecting Fe in aqueous solution³⁺The use of (1).

10. The calixarene-rhodamine supramolecular assembly as claimed in claim 1 as a fluorescent probe for detecting Pb in aqueous solution²⁺The use of (1).

Technical Field

The invention relates to a supramolecular co-assembly and a preparation method and application thereof, in particular to a calixarene-rhodamine supramolecular co-assembly and a preparation method and application thereof.

Background

Supramolecular assembly (Supramolecular assembly) is defined as a group of molecules that are assembled by non-covalent bonds, and can be as simple as two molecules. They may be complex, organized aggregates of spherical, rod-like or sheet-like shapes and retain some integrity, giving them a well-defined microstructure and macroscopic properties.

The application field of supramolecular assembly is wide, such as Samuel 1.Stupp and colleagues of northwest university show that supramolecular assembly of Peptide parent (Peptide amphiphile) into nanofiber can be used for promoting growth of neurons (growth of neurones); and Self-assembly of biological/material science into dendritic dipeptides (Self-assembling dendritic dipeptides) that form empty cylinders assembled in solution or monolith materials. The cylindrical assembly has an internal helical structure and a crystal lattice which is self-organized into a cylindrical shape. Inserted in a membrane with small bubbles, a porous cylindrical assembly mediates proton transport into the entire membrane. Self-assembled dendritic supramolecules have been used as arrangements of nanowires; the electronic sending-receiving component is composed of a cylindrical supermolecular component which can be further self-organized into a two-dimensional columnar liquid lattice; each cylindrical supramolecular assembly functions as a separate wire. High charge carrier mobilities for holes and electrons can be obtained.

The application of the supermolecular assembly fluorescent material researched by the project group for a long time in the aspect of being used as a detection reagent is greatly developed, the supermolecular assembly fluorescent material not only has the advantages of rapidness and effectiveness in detection, good selectivity, high sensitivity and the like, but also has the advantages of low detection cost, low equipment requirement and the like, and is widely popularized and applied in the related fields of detecting harmful substances related to environment and humanity.

It is well known that trace amounts of metal ions are generally necessary for biological metabolism, and that excessive amounts of metal ions can cause significant harm to the human body and the biological environment. For example, although iron ions are very active in metabolic processes such as cellular metabolism, oxygen transport, and electron transfer, excessive iron ions can cause great harm to nucleic acids and proteins. Also, with the widespread industrial use of palladium ions, the environmental pollution caused by palladium ions is becoming more serious. Recent studies have shown that palladium is the second largest metal sensitizer next to nickel metal ions, and its complexation can inhibit the normal function of biological cells. The detection and removal of heavy metal ion pollutants in water are always difficult problems of environmental management. Therefore, the search for novel fluorescent detection agents to rapidly and selectively detect these metal ions remains an important but challenging research topic.

Disclosure of Invention

The invention aims to provide a calixarene-rhodamine supramolecular assembly and a preparation method and application thereof. The supermolecule co-assembly can be used as a fluorescent detection reagent for iron ions and palladium ions in an aqueous solution, and has the advantages of quick and effective detection, good selectivity, high sensitivity, low detection cost and low requirement on equipment.

The technical scheme of the invention is as follows: calixarene-rhodamine supramolecular assembly with molecular formula of C₁₁₂H₁₀₃O₅₁N₂S₁₂The chemical structural formula is shown in figure 1.

The method for preparing the calixarene-rhodamine supramolecular assembly is characterized in that rhodamine and 4-sulfonyl calix [4] arene are used as raw materials and are subjected to co-assembly to prepare the calixarene-rhodamine supramolecular assembly.

The method for preparing the calixarene-rhodamine supramolecular assembly comprises the following steps:

1) mixing rhodamine and 4-sulfonyl calix [4] arene hydrate, adding the mixture into a hydrochloric acid solution, and stirring to dissolve the mixture to obtain a solution A;

2) adding the solution A into an autoclave, carrying out constant-temperature reaction under a heating condition, cooling to room temperature, and standing for crystallization to obtain a crystal B;

3) filtering out the crystal B in the step 2), wherein the crystal B is the calixarene-rhodamine supermolecular assembly.

In the method for preparing calixarene-rhodamine supramolecular assembly, the ratio of the amounts of the rhodamine and the 4-sulfonyl calix [4] arene substances is less than 1: 3.

in the aforementioned method for preparing calixarene-rhodamine supramolecular assemblies, the ratio of the amounts of the rhodamine and 4-sulfonyl calix [4] arene substances is equal to 1: 3.

in the method for preparing the calixarene-rhodamine supramolecular assembly, the concentration of the hydrochloric acid solution in the step 1) is 6 mol/L.

In the method for preparing the calixarene-rhodamine supramolecular assembly, the final heating temperature in the step 2) is 95-105 ℃, and the constant temperature time is 0.5-1.5 h; the standing time is 1-3 d.

In the method for preparing the calixarene-rhodamine supramolecular assembly, the molecular weight of the crystal B is 2713.17.

The calixarene-rhodamine supramolecular assembly is used as a fluorescent probe for detecting Fe in aqueous solution³⁺The use of (1).

The calixarene-rhodamine supramolecular assembly is used as a fluorescent probe for detecting Pb in aqueous solution²⁺The use of (1).

The invention has the advantages of

The calixarene-rhodamine supramolecular assembly can be used as a fluorescence detection reagent to detect Fe in aqueous solution³⁺And Pb²⁺The detection process has the advantages of rapidness, effectiveness, good selectivity on a detected object, high detection sensitivity, low detection cost and low requirement on equipment.

Quantitative analysis experiment

The calixarene-rhodamine supermolecule co-assembly prepared by the invention is prepared into a fluorescent probe standard solution (the concentration is 5 multiplied by 10)^-6mol/L) and then Fe in different amounts of substance is added³⁺The results of the detection with the solution of (4) are shown in FIG. 6, and follow Fe³⁺Is increased, and at 582.05, the fluorescence intensity of the fluorescent probe system continues to decrease until Fe³⁺When the concentration of (A) is 40 times of the concentration of the fluorescent probe, the change of the fluorescence intensity is balanced, and Fe³⁺The linear range of detection is (0-200. mu. mol/L) and the detection limit is 3.08. mu. mol/ml-L。

The calixarene-rhodamine supermolecule co-assembly prepared by the invention is prepared into a fluorescent probe standard solution (the concentration is 5 multiplied by 10)^-6mol/L) and then Pd in amounts of different substances is added²⁺The detection results are shown in FIG. 7, which are associated with Pd²⁺Is increased, and at 582.05, the fluorescence intensity of the fluorescent probe system continues to decrease until Pd²⁺When the concentration of (2) reaches 100 times of the concentration of the fluorescent probe, the change of the fluorescence intensity reaches balance, and Pd²⁺The linear range of detection is (0-500. mu. mol/L), and the detection limit is 7.35. mu. mol/L.

Anti-interference experiment

Preparing a metal ion solution, wherein the metal ions respectively comprise: lithium (Li)⁺) Sodium, sodium (Na)⁺) Potassium (K)⁺) Cesium (Cs)⁺) Magnesium (Mg)^{2 +}) Manganese (Mn)²⁺) Strontium (Sr)²⁺) Barium (Ba)²⁺) Chromium (Cr)³⁺) Iron (Fe)³⁺) Cobalt (Co)²⁺) Nickel (Ni)²⁺) Calcium (Ca)²⁺) Zinc (Zn), zinc (Zn)^{2 +}) Palladium (Pd)²⁺) Rubidium (Rb)²⁺) Iron (Fe)²⁺) Copper (Cu)²⁺) Mercury (Hg) and mercury (Hg)²⁺) And cadmium (Cd)²⁺). The molar concentration of the prepared metal ion solution is 0.2 mol/L.

Taking 18 standard solutions of fluorescent probe (volume 3mL, concentration 5X 10)^-6mol/L) is added into the system, and 40 times of Fe is added into the system³⁺The solution (volume is 3 mu L, concentration is 0.2mol/L) enables a fluorescent probe system to detect Fe³⁺Saturated state is reached, and then 18 kinds of metal ion solutions [ lithium (Li) ] are added into the system respectively⁺) Sodium, sodium (Na)⁺) Potassium (K)⁺) Cesium (Cs)⁺) Magnesium (Mg)²⁺) Manganese (Mn)^{2 +}) Strontium (Sr)²⁺) Barium (Ba)²⁺) Chromium (Cr)³⁺) Cobalt (Co)²⁺) Nickel (Ni)²⁺) Calcium (Ca)²⁺) Zinc (Zn), zinc (Zn)²⁺) Rubidium (Rb)²⁺) Iron (Fe)^{2 +}) Copper (Cu)²⁺) Mercury (Hg) and mercury (Hg)²⁺) And cadmium (Cd)²⁺)](volume: 3. mu.L, concentration: 0.2mol/L), the results are shown in FIG. 8Shown that when sufficient Fe is added to the fluorescent system³⁺The fluorescence is obviously reduced, 18 metal ions are continuously added into the system, the fluorescence of the system is not changed, and the fact that other metal ions cannot detect Fe in the system is proved³⁺Interference is generated.

Taking 18 standard solutions of fluorescent probe (volume 3mL, concentration 5X 10)^-6mol/L), 18 kinds of metal ion solutions [ lithium (Li) ] are respectively added into the system⁺) Sodium, sodium (Na)⁺) Potassium (K)⁺) Cesium (Cs)⁺) Magnesium (Mg)²⁺) Manganese (Mn)²⁺) Strontium (Sr)²⁺) Barium (Ba)²⁺) Chromium (Cr)³⁺) Cobalt (Co)²⁺) Nickel (Ni)²⁺) Calcium (Ca)²⁺) Zinc (Zn), zinc (Zn)²⁺) Rubidium (Rb)²⁺) Iron (Fe)²⁺) Copper (Cu)²⁺) Mercury (Hg) and mercury (Hg)²⁺) And cadmium (Cd)²⁺)](volume: 3. mu.L, concentration: 0.2mol/L), molar amount of metal ion in the support system: molar amount of fluorescent probe 40: 1, then adding 40 times of Fe to the phosphor system³⁺. As shown in FIG. 9, when 18 kinds of metal ions were added to the system, the change in fluorescence intensity was less than 7% at 582.05, and Fe was added continuously³⁺The change value of the fluorescence intensity reaches 88.38 percent, which shows that the fluorescence system can sensitively detect Fe even in the presence of other metal ions³⁺It is clear that other metal ions will not detect Fe to the system³⁺Interference is generated.

Taking 18 standard solutions of fluorescent probe (volume 3mL, concentration 5X 10)^-6mol/L) of Pd, 100 times of Pd is added into the system²⁺The solution (volume is 7.5 mu L, concentration is 0.2mol/L) allows the fluorescent probe system to detect Pd²⁺Saturated state is reached, and then 18 kinds of metal ion solutions [ lithium (Li) ] are added into the system respectively⁺) Sodium, sodium (Na)⁺) Potassium (K)⁺) Cesium (Cs)⁺) Magnesium (Mg)²⁺) Manganese (Mn)²⁺) Strontium (Sr)²⁺) Barium (Ba)²⁺) Chromium (Cr)³⁺) Cobalt (Co)²⁺) Nickel (Ni)²⁺) Calcium (Ca)²⁺) Zinc (Zn), zinc (Zn)²⁺) Rubidium (Rb)²⁺) Iron (Fe)²⁺) Copper (Cu)²⁺) Mercury (Hg) and mercury (Hg)²⁺) And cadmium (Cd)²⁺)](volume is 7.5. mu.L, concentration is 0.2mol/L), the detection result is shown in FIG. 10, when sufficient Pd is added into the fluorescent system²⁺The fluorescence is obviously reduced, 18 metal ions are continuously added into the system respectively, the fluorescence of the system is not changed, and the other metal ions are proved not to detect Pd on the system²⁺Interference is generated.

Taking 18 standard solutions of fluorescent probe (volume 3mL, concentration 5X 10)^-6mol/L), 18 kinds of metal ion solutions [ lithium (Li) ] are respectively added into the system⁺) Sodium, sodium (Na)⁺) Potassium (K)⁺) Cesium (Cs)⁺) Magnesium (Mg)²⁺) Manganese (Mn)²⁺) Strontium (Sr)²⁺) Barium (Ba)²⁺) Chromium (Cr)³⁺) Cobalt (Co)²⁺) Nickel (Ni)²⁺) Calcium (Ca)²⁺) Zinc (Zn), zinc (Zn)²⁺) Rubidium (Rb)²⁺) Iron (Fe)²⁺) Copper (Cu)²⁺) Mercury (Hg) and mercury (Hg)²⁺) And cadmium (Cd)²⁺)](volume: 7.5. mu.L, concentration: 0.2mol/L), molar amount of metal ion in the support system: the molar weight of the fluorescent probe is 100: 1, then adding 100 times of Pd to the phosphor system²⁺. As shown in FIG. 11, when 18 kinds of metal ions were added to the system, the change in fluorescence intensity was less than 7% at 582.05, and Pd was added continuously²⁺The change value of the fluorescence intensity reaches 79.29 percent, which shows that the fluorescence system can sensitively detect Pd even in the presence of other metal ions²⁺It is clear that other metal ions will not detect Pd on the system²⁺Interference is generated.

Drawings

FIG. 1 is a molecular structural formula of a calixarene-rhodamine co-assembly;

FIG. 2 is a molecular structure diagram of calixarene and rhodamine, where a and b are calixarenes and c and d are rhodamine;

FIG. 3 is a single crystal structure diagram of a calixarene-rhodamine co-assembly;

FIG. 4 shows calixarene-rhodamine co-assembly¹HNMR spectra;

FIG. 5 shows the detection of Fe by calixarene-rhodamine fluorescent probe³⁺And Pd²⁺The fluorescence spectrum of (a);

FIG. 6 shows the detection of Fe by calixarene-rhodamine fluorescent probe³⁺The fluorescence spectrum of (a);

FIG. 7 is a diagram of detection of Pd by calixarene-rhodamine fluorescent probe²⁺The fluorescence spectrum of (a);

FIG. 8 shows that other metal ions detect Fe by calixarene-rhodamine fluorescent probe³⁺Interference fluorescence map of (a);

FIG. 9 shows that Fe exists in the coexistence of calixarene-rhodamine fluorescent probe and other metal ions³⁺Fluorescence detection of the system;

FIG. 10 shows other metal ions detecting Pd on calixarene-rhodamine fluorescent probe²⁺Interference fluorescence map of (a);

FIG. 11 shows Pd under the coexistence of calixarene-rhodamine fluorescent probe and other metal ions²⁺Fluorescence detection of the system.

Detailed Description

The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention.

Examples of the invention

Example 1: preparing a calixarene-rhodamine co-assembly:

a. mixing rhodamine (50mg, 0.104mmol) and 4-sulfonyl calix [4] arene hydrate (225mg, 0.302mmol), adding the mixture into a hydrochloric acid solution (6mol/L, 15mL), and stirring to dissolve the mixture to obtain a solution A;

b. transferring the solution A into a stainless steel autoclave with a lining of 25mL of polytetrafluoroethylene, keeping the temperature at 100 ℃ for 1 hour, cooling to room temperature, transferring the solution A into a beaker, and standing at room temperature for 2 days to obtain a crystal B;

c. performing structure test on the crystal B by using a Bruker D8 VENTURE single crystal diffractometer, and determining the molecular configuration and the molecular formula of the crystal B, wherein the molecular configuration is a solid triangular structure, and the molecular formula is C₁₁₂H₁₀₃O₅₁N₂S₁₂Cl, molecular weight 2713.17;

d. determination of Crystal B¹H NMR spectrogram, and further determining the proportion of the calixarene-rhodamine co-assemblyThe ratio of the amount of the substance is rhodamine: calixarenes 1: 3;

e. and filtering and collecting the crystal B (100mg), wherein the crystal B is a fluorescent probe for detecting iron and palladium ions in water.

Example 2: preparing a calixarene-rhodamine co-assembly:

1) mixing rhodamine and 4-sulfonyl calix [4] arene hydrate according to the mass ratio of less than 1: 5, mixing and adding the mixture into a hydrochloric acid solution with the concentration of 6mol/L, and stirring the mixture to dissolve the mixture to obtain a solution A;

2) adding the solution A into an autoclave, keeping the temperature constant for 1.5h under the heating condition of 95 ℃, then cooling the solution A to room temperature, and standing for 1d for crystallization to obtain a crystal B;

3) filtering out the crystal B in the step 2), wherein the crystal B is the calixarene-rhodamine supermolecular assembly.

Example 3: preparing a calixarene-rhodamine co-assembly:

1) mixing rhodamine and 4-sulfonyl calix [4] arene hydrate according to the mass ratio of less than 1: 7, mixing and adding the mixture into a hydrochloric acid solution with the concentration of 6mol/L, and stirring the mixture to dissolve the mixture to obtain a solution A;

2) adding the solution A into an autoclave, keeping the temperature constant for 0.5h under the heating condition of 105 ℃, then cooling the solution A to room temperature, and standing for 3d for crystallization to obtain a crystal B;

3) filtering out the crystal B in the step 2), wherein the crystal B is the calixarene-rhodamine supermolecular assembly.

Example 4: preparing a calixarene-rhodamine fluorescent probe:

the calixarene-rhodamine co-assembly prepared in the example 1 is taken and dissolved with secondary water to obtain a fluorescent probe standard solution with the concentration of (5X 10)^-6mol/L)。

Example 5: calixarene-rhodamine fluorescent probe system for Fe³⁺Detection of (2):

to the standard solution of the fluorescent probe prepared in example 4 (volume: 3ml, concentration: 5X 10)^-6mol/L) of Fe in amounts of different substances³⁺The solution of (1) was tested, (Fe was added)³⁺Has a concentration of 0.2mol/L and a volume of 0.15, 0.3, 0.45. 0.6, … … 3 μ L), with Fe³⁺Is increased, and at 582.05, the fluorescence intensity of the fluorescent probe system continues to decrease until Fe³⁺When the concentration of the fluorescent probe reaches 40 times of the concentration of the fluorescent probe, the change of the fluorescence intensity reaches balance, the change value of the fluorescence intensity reaches 88.38 percent, and the Fe content is³⁺The linear range of detection is (0-200. mu. mol/L), and the detection limit is 3.08. mu. mol/L.

Example 6: calixarene-rhodamine fluorescent probe system for Pb²⁺Detection of (2):

to the standard solution of the fluorescent probe prepared in example 4 (volume: 3ml, concentration: 5X 10)^-6mol/L) of Pb in amounts of different substances²⁺The solution of (1), (with addition of Pb) was tested²⁺Has a concentration of 0.2mol/L and a volume of 0.15, 0.3, 0.45, 0.6, … … 7.5.5. mu.L), with Pb²⁺Is increased, and at 582.05 the fluorescence intensity of the fluorescent probe system continues to decrease until Pb²⁺When the concentration of the fluorescent probe reaches 100 times of the concentration of the fluorescent probe, the change of the fluorescence intensity reaches balance, the change value of the fluorescence intensity reaches 79.29 percent, and Pb is contained²⁺The linear range of detection is (0-500. mu. mol/L), and the detection limit is 7.35. mu. mol/L.

Example 7: detecting a liquid to be detected by a calixarene-rhodamine fluorescent probe system:

standard solution of fluorescent probe prepared in example 4 (volume 3ml, concentration 5X 10)^-6mol/L) is added into the solution to be detected, when the change value of the fluorescence intensity of the system at 582.05 is less than 7%, the system is proved not to contain iron and palladium ions, and when the change value of the fluorescence intensity of the system at 582.05 is more than 7%, the system is proved to contain iron or palladium ions.

The above description is only for the purpose of illustrating the present invention and the appended claims, and the scope of the present invention is not limited thereto, and any person skilled in the art can substitute or change the technical solution and the inventive concept of the present invention within the technical scope of the present invention.