阅读说明：本技术 一种手性硫化铜超粒子的合成方法 (Synthesis method of chiral copper sulfide super particle ) 是由 胥传来 高锐 匡华 徐丽广 马伟 刘丽强 孙茂忠 吴晓玲 宋珊珊 胡拥明 郝昌龙 于 2020-04-23 设计创作，主要内容包括：一种手性硫化铜超粒子的合成方法,属于纳米材料和自组装科学技术领域。本发明以青霉胺稳定的手性硫化亚铜纳米团簇,与烟草花叶病毒衣壳蛋白在光的作用下发生自组装,制备得到饼状的手性硫化铜超粒子。本发明方法提出了一种光控的手性硫化铜超粒子的制备方法,对于开发更多的手性材料和了解手性材料之间的相互作用具有重要的意义。(A method for synthesizing chiral copper sulfide super particles belongs to the technical field of nano materials and self-assembly science. According to the method, the cake-shaped chiral copper sulfide super-particles are prepared by self-assembling the chiral cuprous sulfide nanocluster with stable penicillamine and the capsid protein of the tobacco mosaic virus under the action of light. The method provides a preparation method of optically-controlled chiral copper sulfide super-particles, and has important significance for developing more chiral materials and understanding the interaction between the chiral materials.)

1. A method for synthesizing chiral copper sulfide super particles is characterized in that: the cake-shaped chiral copper sulfide super-particles are prepared by self-assembling the stable chiral cuprous sulfide nanoclusters with tobacco mosaic virus capsid protein under the action of light.

2. The method for synthesizing the chiral copper sulfide super particle according to claim 1, wherein the preparation method of the penicillamine-stabilized chiral cuprous sulfide nanocluster is as follows:

(1) 50mL of ultrapure water were first heated to 60 ℃ under argon and maintained for 30min to exclude oxygen, after which 0.67mmol of CuCl was rapidly added via syringe₂·2H₂O; after the solution is completely dissolved, adding 0.83mmol of NaOH, stirring uniformly, quickly adding 0.67mmol of sodium citrate when flocculent suspended matters are generated, clarifying the solution, and continuously adding 0.83mmol of NaBH₄After the solution turns purple red, finally adding 0.67mmol of penicillamine Pen, and slowly turning the solution into brown; after the temperature is stably increased to 95 ℃, reflux stirring is carried out for 30min, the mixture is slowly cooled to room temperature, the reaction is continued overnight, and when the solution turns to mauve again, the reaction is finished;

(2) adding isopropanol solution with volume more than 6 times, centrifuging at 10000rpm for not less than 15min to purify the nanoclusters; drying the obtained precipitate in 0.07-0.1MPa vacuum oven at 65 deg.C, collecting dried powder, vacuum packaging, and preserving at-20 deg.C.

3. The method for synthesizing chiral copper sulfide nanoparticles according to claim 1, wherein: the tobamovirus capsid protein is in a non-discoid configuration.

4. The method for synthesizing chiral copper sulfide nanoparticles according to claim 3, wherein the capsid protein of tobacco mosaic virus with non-discoid configuration is prepared by: mixing 1mL, 2.5mg/mL of tobacco mosaic virus capsid protein with 10 μ L, 1M dithiothreitol DTT or 10 μ L, 1M beta-mercaptoethanol, incubating at 30 deg.C for 30min, ultrafiltering and purifying by 10KDa ultrafiltering tube at 9000rpm for 10min, and repeating the ultrafiltering and purifying steps three times.

5. The method for synthesizing chiral copper sulfide nanoparticles according to claim 1, wherein the self-assembly process comprises the following steps: firstly, weighing 2mg of purified stable chiral cuprous sulfide nanocluster powder for penicillamine, and dissolving the stable chiral cuprous sulfide nanocluster powder in 10mL of ultrapure water; taking out 1mL of dissolved nanoclusters, mixing the dissolved nanoclusters with 1mL of tobacco mosaic virus capsid protein with a non-disc-shaped configuration, transferring the mixed solution into a 5mL of disposable Zeta potential test colorimetric pool, and radiating for 6 hours under 1W laser at the wavelength of 532 nm; after the reaction was completed, isopropanol of 5 times or more volume was added, and the mixture was centrifuged at 7000rpm for 10min, and finally resuspended in ultrapure water to obtain chiral copper sulfide super particles.

Technical Field

The invention relates to a method for synthesizing chiral copper sulfide super particles, belonging to the technical field of nano materials and self-assembly science.

Background

Chirality is a measure of symmetry of a substance, and a substance that cannot overlap its mirror image is a chiral substance. The earliest people discovered chirality and linked it to optical activity were lewis pasteurs. Scientists subsequently found that most biomolecules (proteins, nucleic acids and carbohydrates) were chiral, and also used their chiral recognition, impressive achievements in enantioselective synthesis of small molecules. Chirality is ubiquitous in nature and is an important sign of life on earth. Almost exclusively L-amino acids and D-sugars are used by all organisms as building blocks for proteins and nucleic acids. Chirality is observed in nature at almost all length scales. For example, the chirality or helicity in a mass-free subatomic particle depends on its spin direction and direction of motion. On the other hand, macroscopic chirality is also the specific aspect in our lives, such as the spiral tendrils of various climbing plants, snail spiral shells, where the formation of a unilateral helix affects the reproduction and growth of snails. The scientific community is investing a great deal of effort to elucidate the origin of homochirality, and inorganic chiral nanoparticles have become an important basic concept.

The first inorganic chiral nanoparticle is a glutathione stabilized gold nanocluster. This chiral ligand induced plasmon chirality was later extended to semiconductor nanocrystals, magnetic nanomaterials, and transition metal nanomaterials. In addition to the circular dichroism effect produced by the above chiral molecules induced achiral nanoparticles, chiral effects in metal and semiconductor nanoparticles can be observed by preparing inorganic nanostructures with chiral shapes. In addition, self-assembly of nanoparticles into precise geometries also exhibits good chiral signals.

Self-assembly has been a long sought goal of the nanocology community because in assemblies, individual components strongly influence the overall performance. For the assembly, the functionality comes from the properties of the individual nanoparticles as well as their bulk properties. Although the preparation of chiral materials is well established, little is known about the generation of chirality, the modulation of chiral signals, and the interactions between chiral species. Therefore, if the natural chiral substance protein and the artificially synthesized and induced inorganic nano material are combined, the natural chiral substance protein and the artificially synthesized and induced inorganic nano material can play a greater role in the fields of catalysis, optics, biosensing and the like. Here we propose that two materials interact in chiral configuration to form a super particle, and may have new insights into the preparation and understanding of nanoscale chiral materials. In addition, the high-level structure formed by self-assembly of inorganic nano-materials and organic macromolecules plays a crucial role in all biological systems with drug loading, signal transmission, optical interaction, catalysis and many other functions.

Disclosure of Invention

The invention aims to overcome the defects and provide a method for synthesizing chiral copper sulfide super particles.

The technical scheme of the invention is a synthesis method of chiral copper sulfide super particles, and the super particles are formed by self-assembly of chiral cuprous sulfide nanoclusters and tobacco mosaic virus capsid protein under the action of light, so that the cake-shaped chiral copper sulfide super particles are formed, and the synthesis method has important significance for developing more chiral materials.

The surface of the chiral cuprous sulfide nanocluster is modified with penicillamine for functionalization, and the tobacco mosaic virus capsid protein in assembly does not exist in a disc-shaped configuration. In addition, the strong interaction between the hydrophobic amino acids of the tobamovirus capsid protein and the hydrophobic cuprous sulfide core, and the high free energy of the nanocluster surface promote the tobamovirus capsid protein to form an organic network framework in which the nanoclusters are embedded and assembled into super particles. Furthermore, circular dichroism, which is significantly different from nanoclusters, is exhibited due to strong interactions between nanoclusters and proteins.

Further, the preparation method of the penicillamine-stabilized chiral cuprous sulfide nanocluster comprises the following steps:

(1) 50mL of ultrapure water were first heated to 60 ℃ under argon for 30 minutes to exclude oxygen, and then 0.67mmol of CuCl was rapidly added via syringe₂·H₂O; after the solution is completely dissolved, adding 0.83mmol of NaOH, stirring uniformly, quickly adding 0.67mmol of sodium citrate when flocculent suspended matters are generated, clarifying the solution, and continuously adding 0.83mmol of NaBH₄After the solution turns purple red, finally adding 0.67mmol of penicillamine Pen, and slowly turning the solution into brown; after the temperature is stably increased to 95 ℃, reflux stirring is carried out for 30 minutes, the mixture is slowly cooled to room temperature, the reaction is continuously carried out overnight, and when the solution turns to mauve again, the reaction is finished;

(2) adding isopropanol solution with volume more than 6 times, centrifuging at 10000rpm for not less than 15min to purify the nanoclusters; drying the obtained precipitate in 0.07-0.1MPa vacuum oven at 65 deg.C, collecting dried powder, vacuum packaging, and preserving at-20 deg.C.

Further, the preparation method of the coat protein of the tobacco mosaic virus with the non-disc-shaped configuration comprises the following steps: mixing 1mL and 2.5mg/mL of tobacco mosaic virus capsid protein with 10 mu L and 1M dithiothreitol DTT or 10 mu L and 1M beta-mercaptoethanol, incubating for 30min at 30 ℃, performing ultrafiltration purification for 10min at 9000rpm by using an ultrafiltration tube of 10KDa, and repeating the step of ultrafiltration purification three times.

Further, the self-assembly process is specifically as follows: firstly, weighing 2mg of purified stable chiral cuprous sulfide nanocluster powder for penicillamine, and dissolving the stable chiral cuprous sulfide nanocluster powder in 10mL of ultrapure water; taking out 1mL of dissolved nanoclusters, mixing the dissolved nanoclusters with 1mL of tobacco mosaic virus capsid protein with a non-disc-shaped configuration, transferring the mixed solution into a 5mL of disposable Zeta potential test colorimetric pool, and radiating for 6 hours under 1W laser at the wavelength of 532 nm; after the reaction was completed, isopropanol of 5 times or more volume was added, and the mixture was centrifuged at 7000rpm for 10min, and finally resuspended in ultrapure water to obtain chiral copper sulfide super particles.

The invention has the beneficial effects that: the method provides a method for synthesizing optically-controlled chiral copper sulfide super particles, and has important significance for developing more chiral materials and understanding the interaction between the chiral materials.

Drawings

Figure 1 ultraviolet and circular dichroism spectra of penicillamine stabilized chiral cuprous sulfide nanoparticles.

Figure 2 Transmission Electron Microscopy (TEM) images of penicillamine stabilized chiral cuprous sulfide nanoparticles.

Figure 3X-ray crystal diffractogram of penicillamine stabilized chiral cuprous sulfide nanoparticles.

FIG. 4 is a UV spectrum and a circular dichroism spectrum of a chiral copper sulfide super particle.

FIG. 5 is a transmission electron micrograph and a high-resolution transmission electron micrograph of chiral copper sulfide super particles.

FIG. 6 Transmission Electron microscopy images of the coat protein of the treated tobacco mosaic virus.

Detailed Description

The following examples are provided as further illustration of the invention and are not to be construed as limitations or limitations of the invention. The invention is further illustrated by the following examples.