CN-121974936-A - Copper nanocluster with inhibition effect on rhizoctonia cerealis as well as preparation method and application thereof

CN121974936ACN 121974936 ACN121974936 ACN 121974936ACN-121974936-A

Abstract

The invention relates to an atomic accurate nano copper cluster material, discloses a copper nano cluster with inhibition effect on rhizoctonia cerealis, and a preparation method and application thereof, and belongs to the crossing field of nano material chemistry and biochemistry. According to the invention, 1-benzyl-4, 4' -bipyridine chloride is used as a ligand, and the nano copper cluster with high yield is synthesized by a room temperature volatilizing one-pot method. The chemical formula of the nano copper cluster material is ：[Cu 5 I 4 (L) 8 (I 3 ) 2 ]·(I 3 ) 7 (I 2 ) 2 （L which is 1-benzyl-4, 4' -bipyridine chloride, and is abbreviated as Cu 5 I 4 , belongs to a triclinic system, and the space group is chiral space group P2 1 /m. The nano copper cluster material has good dispersibility and good biocompatibility, has excellent activity of resisting rhizoctonia cerealis, adopts the copper nano clusters as antibacterial active ingredients, fully exerts the quantum size effect and the advantage of high specific surface area, has high copper ion release efficiency, and can inhibit rhizoctonia cerealis by more than 90%.

Inventors

DING QUNSHAN
ZANG SHUANGQUAN
LI LINKE
XIAO MING
ZHENG XIANFU

Assignees

郑州大学
郑州郑氏化工产品有限公司

Dates

Publication Date: 20260505
Application Date: 20260128

Claims (3)

1. A nano copper cluster material is characterized in that the chemical formula is ：[Cu 5 I 4 (L) 8 (I 3 ) 2 ]·(I 3 ) 7 (I 2 ) 2 ,, wherein L is 1-benzyl-4, 4' -bipyridine chloride, which is abbreviated as Cu 5 I 4 , belongs to a triclinic system, and a space group is a chiral space group P2 1 /m,a= 21.2160(3) Å, b = 17.5791(2) Å, c = 24.7935(3) Å, α = 90°, β = 105.9600°, γ = 90°, V = 8890.5(2) Å 3 .
2. The nano copper cluster material of claim 1, wherein the nano copper cluster material is composed of five copper atoms and eight organic ligands, the structure is a binuclear copper complex, a nitrogen-containing heterocyclic organic molecule is taken as a main ligand, a central Cu atom forms a Cu-N coordination bond with an N atom of a heterocyclic skeleton in the ligand to form a basic coordination unit, an I atom in the system is taken as an auxiliary ligand, and forms Cu-I interaction with the Cu atom in a coordination or bridging mode, so that the two Cu coordination units are connected into a whole, and finally the nano copper cluster material is assembled through weak interaction among Cu-N coordination bonds, cu-I bonds and ligand molecules.
3. The use of the nano copper cluster material according to claim 1 or 2, wherein the nano copper cluster material is used as an active ingredient to prepare an antibacterial agent for inhibiting growth of rhizoctonia cerealis.

Description

Copper nanocluster with inhibition effect on rhizoctonia cerealis as well as preparation method and application thereof Technical Field The invention belongs to the crossing field of nano material chemistry and biochemistry, and in particular relates to a copper nanocluster composite material for resisting rhizoctonia cerealis, and a preparation method and application thereof. Background Rhizoctonia cerealis is an important pathogenic bacterium which damages grain crops such as wheat, corn and the like, and can cause diseases such as banded sclerotial blight and the like, so that the crop is reduced in yield and even is in harvest failure. The existing control means mainly comprise agricultural control and chemical control, the agricultural control effect is limited, the chemical bactericide (such as carbendazim) has the problems of residual pollution, enhanced pathogen resistance and the like, and the traditional copper-based bactericide has the defects of large dosage, low action efficiency, easiness in causing soil copper accumulation and the like. The copper nanocluster is used as a novel nanomaterial, has the advantages of quantum size effect and high specific surface area, has high copper ion release efficiency, has antifungal activity far superior to that of the traditional copper-based bactericide, and has less dosage, thereby reducing environmental burden. However, the existing copper nanoclusters have the defects of high surface activity, easiness in oxidation and agglomeration and poor stability, are difficult to stably load on agricultural base materials, have complex preparation process, and limit the large-scale application of the copper nanoclusters in the prevention and treatment of rhizoctonia cerealis. Therefore, developing a copper nanocluster composite material which has uniform particle size, high stability and excellent activity against rhizoctonia cerealis and can be firmly combined with an agricultural substrate and a simple and efficient preparation method are the problems to be solved in the field. Disclosure of Invention Based on the current state of the art, the invention aims to provide an atomic-scale precise nano copper cluster which has high stability and excellent activity against rhizoctonia cerealis and can be firmly combined with an agricultural substrate. In order to achieve the aim of the invention, the chemical formula of the nano copper cluster material is ：[Cu5I4(L)8(I3)2]·(I3)7(I2)2,, which is abbreviated as Cu 5I4 and belongs to a triclinic system, the space group is chiral space group P21/m,a= 21.2160(3) Å,b= 17.5791(2) Å,c= 24.7935(3) Å,α= 90°,β= 105.9600°,γ = 90°,V= 8890.5(2) Å3., wherein L is 1-benzyl-4, 4' -bipyridine chloride, and the molecular structural formula is as follows: The nano copper cluster material is prepared by the following steps: Step 1, synthesis of ligand 1-benzyl-4, 4' -bipyridine chloride 4,4' -Bipyridine and benzyl chloride are dissolved in anhydrous acetonitrile and heated for reflux reaction. After the reaction was completed, the mixture was cooled to room temperature, and a pale blue powder was obtained by suction filtration and dried in vacuo. Step 2, the synthesis of the nano copper cluster Dissolving ligand 1-benzyl-4, 4' -bipyridine chloride in methanol, dissolving and clarifying at room temperature, adding acetonitrile solution of cuprous iodide, stirring at room temperature for reaction, adding distilled water, stirring at room temperature, adding tetrafluoroboric acid, stirring at room temperature for clarifying, volatilizing the clarified solution at room temperature in a dark place after the reaction is finished to obtain crystals, filtering, washing with methanol, and airing at room temperature. The nano copper cluster material consists of five copper atoms and eight organic ligands, the structure is a binuclear copper (Cu) complex, nitrogen-containing heterocyclic organic molecules are used as main ligands, central Cu atoms form Cu-N coordination bonds with N atoms of heterocyclic frameworks in the ligands to form basic coordination units, meanwhile, I atoms in the system are used as auxiliary ligands to form Cu-I interaction with the Cu atoms in a coordination or bridging mode, the two Cu coordination units are connected into a whole, and finally, the metal organic supermolecular structure with a definite space topology is formed through weak interaction among the Cu-N coordination bonds, the Cu-I bonds and ligand molecules (shown in figure 1). The nano copper cluster material has good dispersibility, fully exerts the quantum size effect and the high specific surface area advantages, improves the copper ion release efficiency, enhances the inhibition and killing effects on rhizoctonia cerealis, and simultaneously, modifies biocompatible ligands on the surface of the copper nano clusters, the ligands can be combined with copper atoms on the surface of the copper nano clusters through coordination to form a stable coating str