CN-122007434-A - Metal nano assembly constructed under non-micelle condition and application thereof

Abstract

The invention discloses a metal nano assembly constructed under a non-micelle condition, wherein a metal precursor and a sulfhydryl ligand undergo a reduction reaction in a dispersion system containing a segmented copolymer with a concentration lower than a critical micelle, and the metal nano assembly is formed by in-situ assembly. The technical scheme not only simplifies the preparation process and avoids the dependence on high-concentration surfactant or hard template in the traditional method, but also realizes the effective regulation and control of the structure and in-vivo metabolism behavior of the nano assembly by dynamically regulating the proportion of copper element in the gold-copper alloy. Experimental results show that the prepared nano-assembly has good dispersibility and biocompatibility, can be biodegraded or cleared in vivo over time, solves the problem that the traditional large-size gold nano-particles are easy to accumulate in non-specific organs for a long time, and has important application potential in the fields of biomedical imaging and diagnosis and treatment.

Inventors

• TANG BING
• HUANG DI
• LI XIA
• WEI ZHONGMING
• LIU YUANLI

Assignees

• 桂林理工大学

Dates

Publication Date

20260512

Application Date

20260121

Claims (10)

1. 1. A metal nano assembly constructed under a non-micelle condition is characterized in that a metal precursor and a sulfhydryl ligand undergo a reduction reaction in a dispersion system containing a segmented copolymer with a concentration lower than a critical micelle, and are assembled in situ to form the metal nano assembly; wherein, the mol ratio of the sulfhydryl ligand, the metal precursor and the reducing agent is (1-10): 1 (5-50); the metal precursor is obtained by mixing a copper precursor and a gold precursor; the copper element accounts for 0-80% of the total mole of the copper element and the gold element.
2. 2. The metal nano-assembly according to claim 1, wherein the copper element is present in a ratio of 40-70% in the molar sum of copper element and gold element.
3. 3. The metal nano-assembly according to claim 1, wherein the block copolymer is selected from one or more of Pluronic F127, pluronic F68, pluronic P123.
4. 4. The metal nano-assembly according to claim 1, wherein the thiol ligand is selected from hydrophobic thiol ligands.
5. 5. The metal nano-assembly according to claim 4, wherein the thiol ligand is selected from ethyl mercaptopropionate.
6. 6. The metal nano-assembly according to claim 1, wherein the copper precursor is selected from at least one of copper nitrate, copper sulfate or copper chloride.
7. 7. The metal nano-assembly according to claim 1, wherein the gold precursor is selected from chloroauric acid or salts thereof.
8. 8. The metal nano-assembly according to claim 1, wherein the reducing agent is selected from the group consisting of lithium borohydride, sodium borohydride, and potassium borohydride.
9. 9. The metal nano-assembly according to any one of claims 1-8, wherein the metal nano-assembly is prepared by a method comprising: 1) Dissolving Pluronic F127 in deionized water, then adding ethyl mercaptopropionate, and fully and uniformly mixing to form a uniform F127/mercapto ligand mixed solution; 2) And then adding a metal precursor into the uniform F127/mercapto ligand mixed solution, wherein the ratio of copper element in the metal precursor to the sum of the moles of copper element and gold element is 40-70%, uniformly stirring, and adding sodium borohydride to enable the mole ratio of mercapto ligand to metal precursor to reducing agent to be 4:1:10, so that a reduction reaction occurs to obtain the metal nano assembly.
10. 10. Use of the metal nano-assembly according to claim 1 for the preparation of a biological imaging material.

Description

Metal nano assembly constructed under non-micelle condition and application thereof Technical Field The invention belongs to the technical field of nano materials and biomedical materials, and particularly relates to a metal nano assembly constructed under a non-micelle condition and application thereof. Background The metal nano material has important application prospect in the fields of biological imaging, diagnosis and treatment integration, drug delivery and the like due to the unique optical, electrical and biological compatibility characteristics. In recent years, novel assembly composite materials constructed by gold nanoparticles as primitives are widely focused by scientists due to the unique optical properties exhibited. Gold nanoparticle assemblies of different morphology and function have been successfully made. Compared with single gold nanoparticles, the gold nanoparticle assembly emits light more strongly in the near infrared band, so that the gold nanoparticle assembly has more important application in the fields of biology, medicine and the like. In addition, the nano composite structure assembled by the gold nano particles and the block polymer not only can integrate the functions of each structural element, but also can have new properties and functions, and provides an effective and feasible way for constructing the multifunctional nano composite material. However, conventional preparation methods generally rely on high concentration of surfactants or hard templates to construct stable nanostructures, and the large-sized AuNPs or AuNAs, which are difficult to biodegrade and are obtained by the preparation method, have strong interactions with liver non-parenchymal cells, and tend to generate non-specific organ accumulation, thus limiting further application of the preparation method. And this not only increases the cost, but the surfactant has some impediment to the later use of the nano-assembly. For example, a large amount of reducing agent and surfactant can not only make the background signal of the nano-assembly too high and be unfavorable for detecting trace substances, but also prevent the active site of the nano-assembly from contacting with the reactant or the detected substance, thus reducing the reaction efficiency and the detection sensitivity. Therefore, the development of a novel preparation strategy for constructing a stable nano assembly under mild conditions and simultaneously having adjustable in-vivo behaviors has important significance. Disclosure of Invention The invention aims to overcome at least one defect of the prior art and provides a metal nano assembly constructed under a non-micelle condition and application thereof. The technical scheme adopted by the invention is as follows: In a first aspect, the present invention provides a metal nano-assembly constructed under non-micelle conditions, wherein a metal precursor and a thiol ligand undergo a reduction reaction in a dispersion system containing a block copolymer with a concentration lower than a critical micelle concentration, and are assembled in situ to form the metal nano-assembly; wherein, the mol ratio of the sulfhydryl ligand, the metal precursor and the reducing agent is (1-10): 1 (5-50); the metal precursor is obtained by mixing a copper precursor and a gold precursor; the copper element accounts for 0-80% of the total mole of the copper element and the gold element. In some embodiments, the copper element is present in a ratio of 40-70% of the molar sum of copper element and gold element. In some embodiments, the block copolymer is selected from one or more of Pluronic F127, pluronic F68, pluronic P123. In some embodiments, the thiol ligand is selected from hydrophobic thiol ligands. In some embodiments, the sulfhydryl ligand is selected from ethyl mercaptopropionate. In some embodiments, the copper precursor is selected from at least one of copper nitrate, copper sulfate, or copper chloride. In some embodiments, the gold precursor is selected from chloroauric acid or salts thereof. In some embodiments, the reducing agent is selected from lithium borohydride, sodium borohydride, or potassium borohydride. In some embodiments, the method of preparing the metal nano-assembly comprises: 1) Dissolving Pluronic F127 in deionized water, then adding ethyl mercaptopropionate, and fully and uniformly mixing to form a uniform F127/mercapto ligand mixed solution; 2) And then adding a metal precursor into the uniform F127/mercapto ligand mixed solution, wherein the ratio of copper element in the metal precursor to the sum of the moles of copper element and gold element is 40-70%, uniformly stirring, and adding sodium borohydride to enable the mole ratio of mercapto ligand to metal precursor to reducing agent to be 4:1:10, so that a reduction reaction occurs to obtain the metal nano assembly. In a second aspect, the invention provides the use of a metal nano-assembly according to the first aspect of the inventio