Hollow nucleobase coordination polymer nano-enzyme and preparation method thereof

Abstract

The invention discloses a hollow nucleobase coordination polymer nano-enzyme and a preparation method thereof. The method mainly comprises the following steps: by taking HAuCl4 as a gold ion source and adenine as a ligand, under the condition of stirring at room temperature for 8 minutes, synthesizing a novel base polymer nano-enzyme based on gold ions and adenine through coordination. Wherein the ratio of HAuCl4 to adenine is strictly kept at 1: 4, and products with irregular shapes are prevented from being formed. The hollow base polymer nano-enzyme containing the hollow structure can be accurately obtained by directly washing with 50% ethanol aqueous solution without additional soft and hard templates. The invention provides a simple rapid coordination synthesis strategy of the hollow coordination polymer nano-enzyme, the process is simple, the condition is mild, and the repeatability is high. The cascade catalytic reaction is realized by encapsulating the guest agent, and the catalytic activity of the hollow coordination polymer nano-enzyme is improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of nanozymes and preparation thereof, and specifically relates to a hollow nucleobase coordinated polymer nanozyme and a preparation method thereof. Background Art

[0002] Nanozymes are nanocatalysts with enzyme-like properties, which are widely used in biosensing, disease treatment and environmental protection due to their cost-effectiveness, stability, scalability and functionalization capabilities. Natural products such as nucleotides, amino acids and peptides have abundant active functional groups and are easy to form bio-coordination polymers with metal ions. They have the advantages of simple preparation methods, environmental friendliness and sensitive response to tumor microenvironment, and are ideal drug-loaded nanozymes.

[0003] Various nanozymes, such as noble metals, metal oxides, and carbon-based materials, have been investigated for catalytic reactive oxygen species therapy for cancer. In catalytic therapy, the integration of multiple components often requires multiple therapeutic schemes. Common strategies involve adsorbing biomolecules onto the surface or pores of nanozymes, but these approaches have limitations related to pore size and environmental factors. Encapsulation strategies can address these challenges, but many nanozyme synthesis methods involve harsh conditions, such as high temperature or alkaline and acidic environments, which may affect the synthesis of nanozymes as well as the encapsulation and activity of biomolecules. Therefore, there is a need to develop green and mild nanozyme synthesis methods that can maintain the activity of biomolecules while achieving effective encapsulation. By exploring environmentally friendly and mild alternative synthetic routes, the performance and applicability of nanozymes in multifunctional catalytic therapy can be potentially improved.

[0004] In view of the above reasons, the present invention is proposed. Summary of the invention

[0005] One of the purposes of the present invention is to provide a hollow nucleobase coordination polymer nanozyme.

[0006] The second object of the present invention is to provide a hollow nucleobase coordination polymer nanozyme and a preparation method thereof.

[0007] The hollow nucleobase coordination polymer nanozyme of the present invention is a hollow structure containing an Au-N3 group.

[0008] The mass ratio of gold element to nitrogen element in the hollow nucleobase coordination polymer nanozyme of the present invention is Au:N=1:2.73.

[0009] The method for forming the hollow structure of the present invention is to directly wash with 50% ethanol aqueous solution.

[0010] The preparation method of the nanozyme with axial coordination of chlorine atoms of the present invention comprises the following steps:

[0011] (1) Adding an adenine aqueous solution into deionized water and then adding an HAuCl4 aqueous solution to obtain a reaction solution;

[0012] (2) After stirring the reaction solution prepared in step (1), the product was dispersed in deionized water and centrifuged. After washing three times, it was dried in a freeze dryer to obtain a nucleobase coordination polymer nanozyme;

[0013] (3) The nucleobase coordination polymer nanozyme obtained in step (2) is washed once with an alcohol solution, washed twice with deionized water, and centrifuged to obtain H nucleobase coordination polymer nanozyme.

[0014] Preferably, the feed ratio of HAuCl4 to adenine in step (1) is strictly maintained at a mass ratio of 1:4.

[0015] Preferably, in step (1), the amount of adenine aqueous solution used is 1 mL and the concentration is 10 mM.

[0016] Preferably, the total amount of deionized water used in step (1) is 10 mL.

[0017] Preferably, in step (1), the amount of HAuCl4 aqueous solution used is 795 μL, and the concentration is 50 mM.

[0018] Preferably, in step (2), the stirring speed is 300 rpm and the stirring time is 8 min.

[0019] Preferably, in step (2), the centrifugal speed is 10000 rpm and the centrifugal time is 7 min.

[0020] Preferably, the alcohol solution in step (3) is an ethanol solution.

[0021] Preferably, in step (3), the alcohol solution concentration is selected to be 50% by volume. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 : Transmission electron microscopy image of the hollow nucleobase coordinated polymer nanozyme described in Example 1 of the present invention.

[0023] Figure 2 : X-ray diffraction pattern of the hollow nucleobase coordinated polymer nanozyme described in Example 1 of the present invention.

[0024] Figure 3 : X-ray photoelectron energy spectrum of the hollow nucleobase coordinated polymer nanozyme described in Example 1 of the present invention.

[0025] Figure 4 : Elemental mapping diagram of the hollow nucleobase coordinated polymer nanozyme described in Example 1 of the present invention.

[0026] Figure 5 : Comparison of the oxidase-like activity of the hollow nucleobase coordinated polymer nanozyme described in Example 1 of the present invention at different pH values.

[0027] Figure 6 : Comparison of the peroxidase activity of the hollow nucleobase coordinated polymer nanozyme described in Example 1 (there is no obvious difference in the enzyme activity of each example, Example 1 is represented here).

[0028] Figure 7 Different alcohols have a significant effect on the shell thickness due to their ease of washing. Figures ad show the shell thickness corresponding to reaction examples 1-4. DETAILED DESCRIPTION

[0029] Next, the technical scheme of the present invention is fully described, and the described embodiments are only preferred embodiments of a part of the present invention, rather than all embodiments. The following examples are only listed as examples of embodiments of the present invention, and do not constitute any limitation to the present invention. Based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative work premise belong to the scope of protection of the present invention. Unless otherwise specified, the reagents and instruments used in the following examples are all commercially available products.

[0030] Example 1

[0031] Prepare a material with a total weight of approximately 30 mg:

[0032] (1) Add adenine aqueous solution (1 mL, 10 mM) into 10 mL of deionized water. Then add HAuCl4 aqueous solution (795 μL, 50 mM) to obtain a reaction solution;

[0033] (2) After stirring the reaction solution prepared in step (1) at 300 rpm for 8 min, the product was dispersed in deionized water and centrifuged at 10,000 rpm for 7 min. After washing three times, the product was dried in a freeze dryer to obtain a nucleobase coordination polymer nanozyme;

[0034] (3) The nucleobase coordination polymer nanozyme obtained in step (2) was washed once with a 50% volume concentration ethanol solution, washed twice with deionized water, and centrifuged to obtain a hollow nucleobase coordination polymer nanozyme with a shell thickness of about 37 nm.

[0035] Example 2

[0036] Prepare a material with a total weight of approximately 30 mg:

[0037] (1) Add adenine aqueous solution (1 mL, 10 mM) into 10 mL of deionized water. Then add HAuCl4 aqueous solution (795 μL, 50 mM) to obtain a reaction solution;

[0038] (2) After stirring the reaction solution prepared in step (1) at 300 rpm for 8 min, the product was dispersed in deionized water and centrifuged at 10,000 rpm for 7 min. After washing three times, the product was dried in a freeze dryer to obtain a nucleobase coordination polymer nanozyme;

[0039] (3) The nucleobase coordination polymer nanozyme obtained in step (2) was washed once with 100% volume concentration ethanol, washed twice with deionized water, and centrifuged to obtain a hollow nucleobase coordination polymer nanozyme with a shell thickness of about 39 nm.

[0040] Example 3

[0041] Prepare a material with a total weight of approximately 30 mg:

[0042] (1) Add adenine aqueous solution (1 mL, 10 mM) into 10 mL of deionized water. Then add HAuCl4 aqueous solution (795 μL, 50 mM) to obtain a reaction solution;

[0043] (2) After stirring the reaction solution prepared in step (1) at 300 rpm for 8 min, the product was dispersed in deionized water and centrifuged at 10,000 rpm for 7 min. After washing three times, the product was dried in a freeze dryer to obtain a nucleobase coordination polymer nanozyme;

[0044] (3) The nucleobase coordination polymer nanozyme obtained in step (2) is washed once with a 50% volume concentration ethylene glycol solution, washed twice with deionized water, and centrifuged to obtain a hollow nucleobase coordination polymer nanozyme with a shell thickness of about 45 nm.

[0045] Example 4

[0046] Prepare a material with a total weight of approximately 30 mg:

[0047] (1) Add adenine aqueous solution (1 mL, 10 mM) into 10 mL of deionized water. Then add HAuCl4 aqueous solution (795 μL, 50 mM) to obtain a reaction solution;

[0048] (2) After stirring the reaction solution prepared in step (1) at 300 rpm for 8 min, the product was dispersed in deionized water and centrifuged at 10,000 rpm for 7 min. After washing three times, the product was dried in a freeze dryer to obtain a nucleobase coordination polymer nanozyme;

[0049] (3) The nucleobase coordination polymer nanozyme obtained in step (2) was washed once with 100% volume concentration methanol, washed twice with deionized water, and centrifuged to obtain a hollow nucleobase coordination polymer nanozyme with a shell thickness of about 50 nm.

Claims

1. A hollow nucleobase coordinated polymer nanozyme, characterized in that: A hollow structure bio-coordination polymer nanozyme containing Au-N3 groups based on gold ions and adenine; the mass ratio of gold element to nitrogen element in the nanozyme is Au:N=1:2.

73.

2. A method for preparing the hollow nucleobase coordinated polymer nanozyme as claimed in claim 1, characterized in that The steps include: (1) adding an aqueous adenine solution into deionized water and then adding an aqueous HAuCl4 solution to obtain a reaction solution; the feed ratio of HAuCl4 to adenine is strictly maintained at a mass ratio of 1:4; (2) stirring the solution prepared in step (1), dispersing the product in deionized water, washing by centrifugation, and drying with a freeze dryer to obtain a base-coordinated polymer nanozyme; (3) The base coordination polymer nanozyme obtained in step (2) is washed once with an alcohol solution, washed with deionized water, and centrifuged to obtain a HAuA CPs hollow nucleobase coordination polymer.

3. The method according to claim 2, characterized in that: The ratio of adenine aqueous solution to deionized water is 1:10, and the concentration is 10 mM.

4. The method according to claim 2, characterized in that: The concentration of the HAuCl4 aqueous solution in step (1) is 50 mM.

5. The method according to claim 2, characterized in that: In step (3), the alcohol solution is selected as ethanol solution.

Images