Synthesis method and application of cucurbituril and derivatives thereof

Abstract

The invention discloses a synthetic method and application of cucurbituril and derivatives, and relates to the field of synthesis of cucurbituril and derivatives, and the synthetic method comprises the following steps: S1, preparing raw materials; s2, carrying out a mixed reaction; and S3, after the reaction is finished, standing and cooling the reaction liquid to room temperature until the cucurbituril and the derivatives thereof are crystallized and separated out. According to the synthetic method and application of the cucurbituril and the derivative thereof, the cucurbituril and the derivative thereof have relatively high rigidity, relatively fixed shape and low possibility of deformation, so that a stable binding site can be provided when the cucurbituril and the derivative thereof are combined with a guest molecule, and the binding effect has very high specificity and predictability; according to the present invention, the specific guest molecule can be accurately identified and selected, the internal cavity is hydrophobic, and the stable inclusion complex can be formed with the guest molecule through the hydrophobic effect of the cavity, the hydrogen-bond interaction of the carbonyl group and the like so as to achieve the functions of guest molecule identification, separation, enrichment and the like.

Description

Technical Field

[0001] The present invention relates to the field of synthesis of cucurbituril and derivatives, and in particular to a synthesis method and application of cucurbituril and derivatives. Background Art

[0002] Cucurbituril is a type of macrocyclic molecule formed by the condensation of glycoluril and formaldehyde. It looks like a gourd or pumpkin, and its inner cavity can complex metal ions or organic ammonium ions.

[0003] When synthesizing cucurbituril and its derivatives, the finished product has poor solubility, which makes it inconvenient to combine with other solvents, and the chemical stability cannot be guaranteed, making it difficult to decompose. Summary of the invention

[0004] The main purpose of the present invention is to provide a synthesis method and application of cucurbituril and its derivatives, which can effectively solve the problems in the background technology.

[0005] To achieve the above object, the technical solution adopted by the present invention is:

[0006] A method for synthesizing cucurbituril and its derivatives comprises the following steps:

[0007] S1: prepare raw materials, glycoluril, aldehyde, acidic ionic liquid and solvent;

[0008] S2: Mixing reaction, mixing glycoluril, aldehyde, acidic ionic liquid and solvent, the reaction temperature is 80°C, the reaction time is 1h, and a reaction solution is obtained;

[0009] S3: After the reaction is completed, the reaction solution is allowed to stand and cool to room temperature until cucurbituril and its derivatives are crystallized.

[0010] Preferably, the acidic ionic liquid includes cations and anions, and the cations of the acidic ionic liquid include but are not limited to imidazolium cations; pyridinium cations; quaternary ammonium cations; quaternary phosphonium cations; piperidinium cations; pyrrole cations; pyrazolium cations; benzimidazolium cations; guanidine cations; thiazolium cations; triazolium cations; sulfonium salt cations; bipyridyl cations; any one of the above, or a mixture of two or more thereof.

[0011] Preferably, the anions of the acidic ionic liquid include but are not limited to chloride ion; bromide ion; iodide ion; sulfate anion; hydrogen sulfate anion; nitrate anion; phosphate anion; hypophosphite anion; tetrafluoroborate anion; hexafluorophosphate anion; arsenic hexafluoride anion; antimony hexafluoride anion; substituted or unsubstituted sulfonic acid anion containing not more than 50 carbon atoms; substituted or unsubstituted aryl sulfonic acid anion containing not more than 50 carbon atoms; substituted or unsubstituted carboxylic acid anion containing not more than 50 carbon atoms; substituted or unsubstituted sulfamide anion containing not more than 50 carbon atoms; substituted or unsubstituted sulfonamide anion containing not more than 50 carbon atoms; substituted or unsubstituted sulfate ester anion containing not more than 50 carbon atoms.

[0012] Preferably, the solvent includes, but is not limited to, water, an inorganic solvent, an organic solvent, a mixture of water and an inorganic solvent, a mixture of water and an organic solvent, and a mixture of an inorganic solvent and an organic solvent.

[0013] Preferably, the organic solvent includes but is not limited to N,N-dimethylformamide, dimethyl sulfoxide, methanol, ethanol, and acetone.

[0014] Preferably, the inorganic solvent includes but is not limited to concentrated sulfuric acid and concentrated hydrochloric acid.

[0015] Preferably, the mass ratio of the acidic ionic liquid to the glycoluril and aldehyde polymer is 1:10000, the molar ratio of the glycoluril and aldehyde is 1:1, and the mass ratio of the total mass of the glycoluril and aldehyde to the solvent is 1:25.

[0016] Disclosed is an application of cucurbituril and its derivatives, wherein the cucurbituril and its derivatives are applied in the fields of medicine, supramolecular chemistry, catalysis, materials science, and environmental science. The medicine field includes applications in drug carriers, drug volume expansion, disease diagnosis, and photothermal therapy; the supramolecular chemistry field includes applications in molecular switches, molecular recognition, and supramolecular assembly; the catalysis field includes applications in simulated enzyme catalysis and catalyst carriers; the materials science field includes applications in intelligent materials and fluorescent materials; and the environmental science field includes applications in sewage treatment, gas adsorption and separation.

[0017] Compared with the prior art, the present invention has the following beneficial effects:

[0018] The cucurbituril and its derivatives prepared by the present invention have high rigidity, and their shapes are relatively fixed and not easy to deform, so that when they are combined with guest molecules, they can provide stable binding sites, and the binding action has strong specificity and predictability, which is conducive to accurately identifying and selecting specific guest molecules. The internal cavity is hydrophobic, and the two ends are open and of the same size. This special cavity structure can accommodate various organic molecules or ions, and through the hydrophobic effect of the cavity and the hydrogen bonding effect of the carbonyl group, etc., it can form a stable inclusion complex with the guest molecule, thereby realizing the functions of identifying, separating and enriching the guest molecule, etc., and at the same time has good chemical stability, and can be used in the absence of It can maintain its structural integrity and performance stability in the same chemical environment, which enables it to withstand certain changes in chemical conditions in various chemical reactions and applications, and is not prone to decomposition or deterioration, thus ensuring its long-term and stable application in multiple fields. It has good selective strong bonding ability with many types of guest molecules. It can accurately select matching guest molecules according to the size, shape, charge distribution and functional groups of the guest molecules to combine with them to form a host-guest complex with specific structure and function. This selective bonding ability provides an important basis for its application in molecular recognition, sensors, drug carriers and other fields. DETAILED DESCRIPTION

[0019] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0020] A method for synthesizing cucurbituril and its derivatives comprises the following steps:

[0021] S1: prepare raw materials, glycoluril, aldehyde, acidic ionic liquid and solvent;

[0022] S2: Mixing reaction, mixing glycoluril, aldehyde, acidic ionic liquid and solvent, the reaction temperature is 80°C, the reaction time is 1h, and a reaction solution is obtained;

[0023] S3: After the reaction is completed, the reaction solution is allowed to stand and cool to room temperature until cucurbituril and its derivatives are crystallized.

[0024] The acidic ionic liquid includes cations and anions. The cations of the acidic ionic liquid include but are not limited to imidazolium cations; pyridinium cations; quaternary ammonium cations; quaternary phosphonium cations; piperidinium cations; pyrrole cations; pyrazolium cations; benzimidazolium cations; guanidine cations; thiazolium cations; triazolium cations; sulfonium salt cations; bipyridyl cations; any one of the above, or a mixture of two or more thereof.

[0025] The anions of the acidic ionic liquid include, but are not limited to, chloride ion; bromide ion; iodide ion; sulfate anion; hydrogen sulfate anion; nitrate anion; phosphate anion; hypophosphite anion; tetrafluoroborate anion; hexafluorophosphate anion; arsenic hexafluoride anion; antimony hexafluoride anion; substituted or unsubstituted sulfonic acid anion containing not more than 50 carbon atoms; substituted or unsubstituted aryl sulfonic acid anion containing not more than 50 carbon atoms; substituted or unsubstituted carboxylic acid anion containing not more than 50 carbon atoms; substituted or unsubstituted sulfamide anion containing not more than 50 carbon atoms; substituted or unsubstituted sulfonamide anion containing not more than 50 carbon atoms; substituted or unsubstituted sulfate ester anion containing not more than 50 carbon atoms.

[0026] The solvent includes, but is not limited to, water, an inorganic solvent, an organic solvent, a mixture of water and an inorganic solvent, a mixture of water and an organic solvent, and a mixture of an inorganic solvent and an organic solvent.

[0027] The organic solvent includes, but is not limited to, N,N-dimethylformamide, dimethyl sulfoxide, methanol, ethanol, and acetone.

[0028] Inorganic solvents include, but are not limited to, concentrated sulfuric acid and concentrated hydrochloric acid.

[0029] The mass ratio of the acidic ionic liquid to the glycoluril and aldehyde polymer is 1:10000, the molar ratio of glycoluril and aldehyde is 1:1, and the mass ratio of the total mass of glycoluril and aldehyde to the solvent is 1:25.

[0030] A use of cucurbituril and its derivatives, wherein the cucurbituril and its derivatives are used in the fields of medicine, supramolecular chemistry, catalysis, materials science, and environmental science. The medicine field includes the use of cucurbituril as a drug carrier: cucurbituril has good chemical stability and low biological toxicity, and its cavity can accommodate drug molecules. It forms inclusion complexes with drugs through non-covalent bonding to achieve targeted release of drugs, thereby improving the efficacy of drugs, reducing the distribution of drugs in non-target tissues, and reducing side effects; drug volume expansion: some poorly soluble drugs can form inclusion complexes with cucurbituril and its derivatives to increase the solubility of drugs, improve the solubility of drugs, and facilitate the absorption of drugs and the preparation of preparations; disease diagnosis: supramolecular systems based on cucurbituril can be used to construct fluorescent probes or biosensors for detecting specific substances or biomarkers in organisms, and assist in the early diagnosis of diseases; photothermal therapy: for example, supramolecular photothermal agents prepared with cucurbituril (8) and dibenzotetrathiafulvalene as raw materials can be used for photothermal ablation of living tumor cells, and have potential application prospects in the field of photothermal therapy;

[0031] The field of supramolecular chemistry includes applications in molecular switches: cucurbituril can be used as a host molecule to form inclusion complexes with guest molecules. By changing external conditions such as temperature, pH, and light, the interaction between the host and the guest changes, thereby realizing the function of the molecular switch. For example, a pH-responsive molecular switch can change cucurbituril from one state to another by adjusting the pH value, and can also be restored to the initial state by thermal activation; molecular recognition: the cavity of cucurbituril has a specific size and chemical environment, and can selectively recognize and bind to guest molecules with suitable size, shape and functional groups, and can be used to separate, enrich and detect specific ions or molecules; supramolecular assembly: cucurbituril and its derivatives can self-assemble with other molecules or nanomaterials through host-guest interactions to form supramolecular aggregates with specific structures and functions, such as supramolecular polymers, nanotubes, nanocapsules, etc. These aggregates have potential application value in materials science, biomedicine and other fields;

[0032] The catalytic field includes applications in enzyme-mimicking catalysis: cucurbituril has enzyme-like properties in certain reactions, which can accelerate the reaction rate, improve the selectivity and efficiency of the reaction, and in cycloaddition reactions, cucurbituril can be used as a catalyst to promote the reaction; catalyst carrier: the composite material formed by cucurbituril and inorganic matrix units can be used as an adsorption material and catalyst carrier, improving the stability and activity of the catalyst and facilitating the recovery and reuse of the catalyst;

[0033] The field of materials science includes applications in smart materials: Cucurbituril-based supramolecular systems can respond to external stimuli such as temperature, pH, light, ion concentration, etc., and can therefore be used to prepare smart materials such as smart sensors, smart membranes, smart gels, etc. These materials have potential application prospects in environmental monitoring, biomedicine, food packaging and other fields; Fluorescent materials: By rationally designing the host-guest system of cucurbituril and fluorescent molecules, multi-color luminescence of a single fluorescent element can be achieved, and organic luminescent materials with controllable fluorescence can be constructed, which can be applied to anti-counterfeiting materials, optical devices and bio-imaging and other fields;

[0034] The field of environmental science includes applications in wastewater treatment: cucurbituril and its derivatives can interact with pollutants in water, such as adsorption and inclusion, to achieve the removal and separation of pollutants. It can be used to treat wastewater containing heavy metal ions, organic pollutants, etc.; gas adsorption and separation: the cavity structure of cucurbituril can accommodate gas molecules. By adjusting the structure and properties of cucurbituril, selective adsorption and separation of specific gases can be achieved, which can be applied to gas storage, separation and purification and other fields. Specific embodiment one:

[0036] A method for synthesizing cucurbituril and its derivatives comprises the following steps:

[0037] S1: prepare raw materials, glycoluril, aldehyde, acidic ionic liquid and solvent, wherein the cation in the acidic ionic liquid is a mixture of sulfonium salt cation and bipyridyl cation, the anion in the acidic ionic liquid is an unsubstituted sulfonic acid anion containing no more than 50 carbon atoms, the solvent is concentrated hydrochloric acid in an inorganic solvent, the mass ratio of the acidic ionic liquid to glycoluril and aldehyde polymer is 1:10000, the molar ratio of glycoluril and aldehyde is 1:1, and the mass ratio of the total mass of glycoluril and aldehyde to the solvent is 1:25;

[0038] S2: Mixing reaction, mixing glycoluril, aldehyde, acidic ionic liquid and solvent, the reaction temperature is 80°C, the reaction time is 1h, and a reaction solution is obtained;

[0039] S3: After the reaction is completed, the reaction solution is allowed to stand and cool to room temperature until cucurbituril and its derivatives are crystallized. Specific embodiment 2:

[0041] A method for synthesizing cucurbituril and its derivatives comprises the following steps:

[0042] S1: prepare raw materials, glycoluril, aldehyde, acidic ionic liquid and solvent, wherein the cation in the acidic ionic liquid is a mixture of pyridinium cation and quaternary ammonium cation, the anion in the acidic ionic liquid is a substituted sulfamide anion containing no more than 50 carbon atoms, the solvent is concentrated sulfuric acid in an inorganic solvent, the mass ratio of the acidic ionic liquid to glycoluril and aldehyde polymer is 1:10000, the molar ratio of glycoluril and aldehyde is 1:1, and the mass ratio of the total mass of glycoluril and aldehyde to the solvent is 1:25;

[0043] S2: Mixing reaction, mixing glycoluril, aldehyde, acidic ionic liquid and solvent, the reaction temperature is 80°C, the reaction time is 1h, and a reaction solution is obtained;

[0044] S3: After the reaction is completed, the reaction solution is allowed to stand and cool to room temperature until cucurbituril and its derivatives are crystallized. Specific embodiment three:

[0046] A method for synthesizing cucurbituril and its derivatives comprises the following steps:

[0047] S1: prepare raw materials, glycoluril, aldehyde, acidic ionic liquid and solvent, wherein the cation in the acidic ionic liquid is guanidine cation, the anion in the acidic ionic liquid is a mixture of hexafluorophosphate anion and arsenic hexafluoride anion, the solvent is dimethyl sulfoxide in an organic solvent, the mass ratio of the acidic ionic liquid to glycoluril and aldehyde polymer is 1:10000, the molar ratio of glycoluril and aldehyde is 1:1, and the mass ratio of the total mass of glycoluril and aldehyde to the solvent is 1:25;

[0048] S2: Mixing reaction, mixing glycoluril, aldehyde, acidic ionic liquid and solvent, the reaction temperature is 80°C, the reaction time is 1h, and a reaction solution is obtained;

[0049] S3: After the reaction is completed, the reaction solution is allowed to stand and cool to room temperature until cucurbituril and its derivatives are crystallized.

[0050] The performance of the cucurbituril and its derivatives prepared by the present invention is compared with that of the cucurbituril and its derivatives prepared by the prior art. The present invention selects the cucurbituril and its derivatives prepared by the specific embodiment 1, which is recorded as embodiment 1, and the prior art is recorded as comparative examples 1-2. The following is a comparison table:

[0051]

[0052]

[0053]

[0054] It can be seen that the cucurbituril and its derivatives prepared in the present application have obvious advantages.

[0055] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A method for synthesizing cucurbituril and its derivatives, characterized in that: The steps include: S1: prepare raw materials, glycoluril, aldehyde, acidic ionic liquid and solvent; S2: Mixing reaction, mixing glycoluril, aldehyde, acidic ionic liquid and solvent, the reaction temperature is 80°C, the reaction time is 1h, and a reaction solution is obtained; S3: After the reaction is completed, the reaction solution is allowed to stand and cool to room temperature until cucurbituril and its derivatives are crystallized.

2. The method for synthesizing cucurbituril and its derivatives according to claim 1, characterized in that: The acidic ionic liquid includes cations and anions, and the cations of the acidic ionic liquid include but are not limited to imidazolium cations; pyridinium cations; quaternary ammonium cations; quaternary phosphonium cations; piperidinium cations; pyrrole cations; pyrazolium cations; benzimidazolium cations; guanidine cations; thiazolium cations; triazolium cations; sulfonium salt cations; bipyridyl cations; any one of the above, or a mixture of two or more thereof.

3. The method for synthesizing cucurbituril and its derivatives according to claim 1, characterized in that: The anions of the acidic ionic liquid include, but are not limited to, chloride ions; bromide ions; iodide ions; sulfate anions; hydrogen sulfate anions; nitrate anions; Phosphate anion; hypophosphite anion; tetrafluoroborate anion; hexafluorophosphate anion; arsenic hexafluoride anion; antimony hexafluoride anion; substituted or unsubstituted sulfonic acid anion containing not more than 50 carbon atoms; substituted or unsubstituted arylsulfonic acid anion containing not more than 50 carbon atoms; substituted or unsubstituted carboxylic acid anion containing not more than 50 carbon atoms; substituted or unsubstituted sulfamide anion containing not more than 50 carbon atoms; substituted or unsubstituted sulfonamide anion containing not more than 50 carbon atoms; substituted or unsubstituted sulfate anion containing not more than 50 carbon atoms.

4. The method for synthesizing cucurbituril and its derivatives according to claim 1, characterized in that: The solvent includes, but is not limited to, water, an inorganic solvent, an organic solvent, a mixture of water and an inorganic solvent, a mixture of water and an organic solvent, and a mixture of an inorganic solvent and an organic solvent.

5. The method for synthesizing cucurbituril and its derivatives according to claim 1, characterized in that: The organic solvent includes, but is not limited to, N,N-dimethylformamide, dimethyl sulfoxide, methanol, ethanol, and acetone.

6. The method for synthesizing cucurbituril and its derivatives according to claim 1, characterized in that: The inorganic solvent includes, but is not limited to, concentrated sulfuric acid and concentrated hydrochloric acid.

7. The method for synthesizing cucurbituril and its derivatives according to claim 1, characterized in that: The mass ratio of the acidic ionic liquid to the glycoluril and aldehyde polymer is 1:10000, the molar ratio of the glycoluril and aldehyde is 1:1, and the mass ratio of the total mass of the glycoluril and aldehyde to the solvent is 1:

25.

8. An application of cucurbituril and its derivatives, using the synthesis method of cucurbituril and its derivatives according to claims 1-7, characterized in that: The cucurbituril and its derivatives are used in the fields of medicine, supramolecular chemistry, catalysis, materials science, and environmental science. The medicine field includes applications in drug carriers, drug volume expansion, disease diagnosis, and photothermal therapy; the supramolecular chemistry field includes applications in molecular switches, molecular recognition, and supramolecular assembly; the catalysis field includes applications in simulated enzyme catalysis and catalyst carriers; the materials science field includes applications in smart materials and fluorescent materials; and the environmental science field includes applications in sewage treatment, gas adsorption and separation.

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