CN-121975134-A - Amorphous copper-cyanuric acid coordination polymer and preparation method and application thereof

Abstract

The invention discloses an amorphous copper-cyanuric acid coordination polymer and a preparation method and application thereof, belonging to the technical field of functional materials and biomimetic catalysis. The polymer does not have a long-range order structure, and the copper element takes monovalent copper as main existing valence state. The preparation method comprises the steps of taking cuprous oxide as a template, carrying out surface coordination reaction with cyanuric acid to form a core-shell intermediate, removing the template through acid etching, and reconstructing to obtain the final amorphous coordination polymer. The material has high-efficiency peroxidase-like and glutathione oxidase-like double-enzyme activities, can synergistically catalyze hydrogen peroxide to generate hydroxyl free radicals and consume glutathione, and can obviously kill cancer cells by inducing a copper death mechanism in a tumor microenvironment. The material has unique structure, excellent catalytic performance, simple and controllable preparation method and wide application prospect in the fields of tumor catalytic treatment, bionic sensing and the like.

Inventors

• CHENG FANG
• WANG XINYUE
• WANG LIANHUI

Assignees

• 南京邮电大学

Dates

Publication Date

20260505

Application Date

20260128

Claims (10)

1. 1. The amorphous copper-cyanuric acid coordination polymer is characterized in that the polymer is prepared from a cuprous oxide template and cyanuric acid by a template-coordination-etching method, the polymer has an amorphous coordination network with an amorphous range order structure, and copper elements in the polymer are mainly monovalent copper.
2. 2. The amorphous copper-cyanuric acid coordination polymer of claim 1, having peroxidase-like activity and glutathione oxidase-like activity.
3. 3. A method for preparing the amorphous copper-cyanuric acid coordination polymer of claim 1, comprising the steps of: Step S1, preparing cuprous oxide nano particles as a template material; Step S2, carrying out coordination reaction on cuprous oxide nano-particles and cyanuric acid in a solvent under a heating condition, and forming a coordination layer on the surfaces of the cuprous oxide nano-particles to obtain an intermediate product; And step S3, etching the intermediate product under an acidic condition to remove the internal cuprous oxide template, thereby obtaining the amorphous copper-cyanuric acid coordination polymer.
4. 4. A method according to claim 3, wherein in step S2, the heating temperature is 60-80 ℃ and the reaction time is 5-10 min.
5. 5. A method according to claim 3, wherein in step S2, the solvent is an ethanol solution containing PVP.
6. 6. A method according to claim 3, wherein in step S3, the acidic condition is a hydrochloric acid solution having a pH of 1 to 2, and the etching time is 2 to 4 h.
7. 7. A method according to claim 3, wherein in step S2, the shell thickness of the final product is controlled by adjusting the molar ratio of cuprous oxide nanoparticles to cyanuric acid.
8. 8. Use of the amorphous copper-cyanuric acid coordination polymer of claim 1 for the preparation of enzyme-like catalysts.
9. 9. The use according to claim 8, wherein the enzyme-like catalyst is used for a peroxidase-like catalytic reaction and/or a glutathione oxidase-catalyzed reaction.
10. 10. Use of the amorphous copper-cyanuric acid coordination polymer of claim 1 for the preparation of a medicament for the treatment of tumors.

Description

Amorphous copper-cyanuric acid coordination polymer and preparation method and application thereof Technical Field The invention relates to the technical field of functional materials and biomimetic catalysis, in particular to an amorphous copper-cyanuric acid coordination polymer, a preparation method and application thereof, and especially relates to application of the material in catalytic reaction of peroxidase-like enzyme and glutathione oxidase. Background The nano enzyme has certain advantages compared with the natural enzyme in the aspects of stability, structure controllability, cost and the like, and has been widely paid attention in the field of biomimetic catalysis in recent years. The catalytic reaction related to the peroxidase-like enzyme and the glutathione oxidase plays an important role in the peroxide conversion and glutathione regulation process, so that the development of an artificial catalytic material with high-efficiency peroxidase-like and glutathione oxidase activities has important significance. The existing enzyme-like catalytic materials are mostly based on crystalline metal oxides (such as Cu 2 O, cuO), metal sulfides or metal organic framework structures. Because the crystalline material has an obvious long-range ordered structure, the types, the number and the spatial distribution of active sites are relatively fixed, and the accessibility of substrates is limited, so that the catalytic efficiency and the kinetic performance are difficult to further improve. In addition, in partial copper-based crystalline materials, the valence stability and the structural reversibility of copper elements are insufficient, and the structural evolution easily occurs in the reaction process, so that the stability and the repeatability of the catalytic performance of the enzyme are affected. In order to break through the limitations of the crystal structure, amorphous materials are receiving attention for their structural features of short-range order and long-range disorder, which structure facilitates exposure of more unsaturated coordination sites and structural defects, thereby significantly increasing the active site density and improving the adsorption and reaction behavior of substrate molecules. However, the existing amorphous enzyme-like materials still have defects in terms of structure construction and controllability, and it is difficult to realize accurate regulation and control of active site distribution and catalytic functions while ensuring stable structure, and particularly in a copper-based material system for simultaneously realizing peroxidase-like catalytic activity and glutathione oxidase-like activity, great challenges are still faced. On the other hand, as nanoenzymes continue to be studied, their controllable catalytic properties have demonstrated potential value in a variety of application studies including tumor therapy. For example, in tumor microenvironments, abnormal levels of peroxide and glutathione provide specific reaction conditions for the application of peroxidase-like enzymes and glutathione oxidase, and higher requirements on material structure and catalytic performance are imposed. Therefore, a copper-based material which is based on an amorphous structure, has abundant active sites and has activities of peroxidase-like enzyme and glutathione oxidase is developed, and the preparation method which is adjustable in structure, simple in process and good in repeatability is provided, so that the method has important research significance and application prospect. Disclosure of Invention Aiming at the problems that the existing enzyme-like catalytic material is generally limited in active site, insufficient in structural controllability, difficult to realize high-efficiency activity of peroxidase-like enzyme and glutathione oxidase and the like, the invention aims to provide an amorphous copper-based coordination polymer material and a preparation method thereof. The material builds an amorphous coordination network through structure regulation and control, and enriches unsaturated copper active sites, so that the material has the catalytic activity of peroxidase-like (POD) and the catalytic activity of glutathione oxidase (GSHOx) at the same time. The invention further aims to provide a preparation method with simple process, mild condition and good repeatability, and the structure and performance of the amorphous copper-based coordination polymer can be controllably constructed through the cooperative regulation and control of template coordination and etching processes. The invention also aims to provide the application of the amorphous copper-based coordination polymer in enzyme-like catalytic reaction, so as to expand the application range of the copper-based coordination material in biomimetic catalysis and related fields and provide a material foundation for the catalytic application of the copper-based coordination material under tumor related microe