CN110625125B - Method for preparing liquid metal nanoparticles by using amino acid as ligand - Google Patents

Abstract

The invention discloses a method for preparing liquid metal nanoparticles by using amino acids as ligands, comprising the following steps: (1) dissolving the amino acid in deionized water to obtain a clear amino acid aqueous solution; (2) adjusting the pH of the amino acid aqueous solution (3) liquid metal and zirconium beads are added dropwise to the pH-adjusted solution, and then oscillated and ground to prepare liquid metal nanoparticles with a particle size of 100-5000 nm. The present invention also provides the liquid metal nanoparticles prepared by the method. The method for preparing liquid metal nanoparticles by using amino acids as ligands of the present invention solves the problems of low production scale and efficiency, large particle size and poor biocompatibility of the existing liquid metal nanoparticles.

Description

A method for preparing liquid metal nanoparticles using amino acids as ligands

technical field

The invention relates to the technical field of liquid metal nanoparticles, in particular to a method for preparing liquid metal nanoparticles by using amino acids as ligands.

Background technique

Liquid metal has the advantages of high flexibility, deformability, low cytotoxicity, easy surface modification, low melting point, easy operation and processing, obvious infrared absorption and temperature rise, and can be degraded in a weakly acidic environment. received more and more attention.

However, liquid metal is denser and has higher surface tension, which is not conducive to dispersing into smaller nanoparticles. And it is quickly oxidized in water or air, and the adjacent particles are easily agglomerated to produce precipitation. Many researchers use various surfactants to modify liquid metal nanoparticles, but most of these surfactants are various chemical substances, which have certain biocompatibility problems. At the same time, most of the existing technologies are based on the ultrasonic method, which can only produce liquid metal nanoparticles in small batches, and the operation is complicated and the particle size of the produced particles is large.

SUMMARY OF THE INVENTION

The object of the present invention is to provide a method for preparing liquid metal nanoparticles using amino acids as ligands, aiming to solve the problems of low production scale and efficiency, large particle size and poor biocompatibility of existing liquid metal nanoparticles. question.

In order to solve the above-mentioned technical problems, the present invention provides a method for preparing liquid metal nanoparticles using amino acids as ligands, comprising the following steps:

(1) dissolving amino acid in deionized water to obtain clear amino acid aqueous solution;

(2) adjusting the pH of the amino acid aqueous solution to 2-10;

(3) adding liquid metal and zirconium beads dropwise to the pH-adjusted solution, and oscillating and grinding to prepare liquid metal nanoparticles with a particle size of 100-5000 nm.

In the present invention, the addition of amino acid is equivalent to a dispersant, which can effectively isolate each small liquid metal particle and prevent its agglomeration and precipitation.

Further, in step (1), the amino acid is cysteine, phenylalanine, lysine, histidine, tryptophan, aspartic acid, leucine, glycine, alanine, One or more of valine, isoleucine, proline, serine, tyrosine, methionine, asparagine, glutamine, threonine, glutamic acid and arginine.

Further, in step (1), the mass ratio of the amino acid to deionized water is (0.1-10):100, preferably 1:100.

Further, in step (3), the liquid metal is one or more of gallium, gallium indium alloy, and gallium indium tin alloy. The gallium, gallium indium alloy, or gallium indium tin alloy can be selected from all commercially available products, and gallium indium alloy and gallium indium tin alloy can also be prepared according to the alloy preparation methods described in the prior art. Preferably, the liquid metal is a gallium indium alloy, more preferably Ga ₆₀ In ₄₀ , Ga ₇₀ In ₃₀ , Ga ₇₅ In ₂₅ , Ga _75.5 In _24.5 , Ga ₈₀ In ₂₀ .

Further, in step (3), the mass ratio of the liquid metal to deionized water is (0.1-10):100, preferably 1:100.

Further, in step (3), the diameter of the zirconium beads is one or more of 0.1-0.2 mm, 0.3-0.4 mm, 0.5-0.6 mm, and 0.8-1 mm.

Further, in step (3), the mass ratio of the added amount of the zirconium beads to the mixed solution is 10:(0.1-10).

Further, in step (3), a vibrating machine is used to vibrate, and the vibrating and grinding time is 1-20 h.

Another aspect of the present invention provides liquid metal nanoparticles prepared by the method.

Beneficial effects of the present invention:

1. The present invention provides a kind of using amino acid as a ligand to efficiently and conveniently prepare liquid metal nanoparticles, which solves the problems of low production scale and efficiency, large particle size and high biocompatibility of existing liquid metal nanoparticles. Bad question. Since different pH has a great influence on the dispersion effect of liquid metal nanoparticles, the ratio of amino acid and liquid metal to solvent, different pH, grinding time, etc. can be flexibly adjusted to obtain liquid metal nanoparticles with different concentrations and particle sizes.

2. The present invention can realize simple and low-cost preparation of liquid metal nanoparticles, which broadens its application in the fields of bioengineering, drug delivery and release, flexible wear, printed circuits, heat dissipation of electronic products, and the like.

Description of drawings

Fig. 1 is a photograph of the liquid metal nanoparticle suspension obtained when the pH values of cysteine, phenylalanine and lysine aqueous solutions are respectively 3, 5, 7 and 9;

FIG. 2 is a particle size distribution diagram of the liquid metal nanoparticles when the pH=7 of the cysteine solution, the pH=3 of the phenylalanine solution, and the pH=3 of the lysine solution.

Detailed ways

The present invention will be further described below with reference to the accompanying drawings and specific embodiments, so that those skilled in the art can better understand the present invention and implement it, but the embodiments are not intended to limit the present invention.

Example 1

This embodiment provides a method for preparing liquid metal nanoparticles using amino acids as ligands, which specifically includes the following steps:

(1) get 100g deionized water in glass bottle, get 1g cysteine and dissolve in deionized water, obtain transparent clear solution;

(2) Adjust the pH of the solution in (1) to 7, and add 1 g of liquid metal (Ga ₇₅ In ₂₅ ).

(3) Add 300 g of zirconium beads with a diameter of 0.3 to 0.4 mm to the solution in step (2), and shake in a vibrating mill for 2 hours to obtain liquid metal nanoparticles with a particle size of 300 nm.

Example 2

This embodiment provides a method for preparing liquid metal nanoparticles using amino acids as ligands, which specifically includes the following steps:

(1) get 100g deionized water in glass bottle, get 1g lysine and dissolve in deionized water, obtain transparent clear solution;

(2) The pH of the solution in (1) was adjusted to 3, and 1 g of liquid metal (Ga ₇₅ In ₂₅ ) was added.

(3) 300g of zirconium beads with a diameter of 0.3-0.4 mm are added to the solution in step (2), and shaken in a vibrating mill for 2 hours to obtain liquid metal nanoparticles with a particle size of 250 nm.

Example 3

This embodiment provides a method for preparing liquid metal nanoparticles using amino acids as ligands, which specifically includes the following steps:

(1) Get 100g deionized water in a glass bottle, get 1g phenylalanine and dissolve it in deionized water, heat and stir at 50°C to obtain a transparent clear solution;

(2) The pH of the solution in (1) was adjusted to 3, and 1 g of liquid metal (Ga ₇₅ In ₂₅ ) was added.

(3) Add 300 g of zirconium beads with a diameter of 0.3 to 0.4 mm to the solution in step (2), and shake in an oscillating mill for 2 hours to obtain liquid metal nanoparticles with a particle size of 200 nm.

Example 4

The difference between this example and Example 1 is only that the pH in step (2) of Example 1 is adjusted to 6.

Example 5

The difference between this example and Example 2 is only that the pH in step (2) of Example 2 is adjusted to 2.

Example 6

The difference between this example and Example 3 is only that the pH in step (2) of Example 3 is adjusted to 2.

Example 7

The difference between this embodiment and Embodiment 3 is only that the liquid metal in step (2) of Embodiment 3 is replaced with Ga ₆₀ In ₄₀ .

Example 8

The difference between this embodiment and Embodiment 3 is only that the liquid metal in step (2) of Embodiment 3 is replaced with Ga ₇₀ In ₃₀ .

Example 9

The difference between this embodiment and Embodiment 3 is only that the liquid metal in step (2) of Embodiment 3 is replaced with Ga _75.5 In _24.5 .

Example 10

The difference between this embodiment and Embodiment 3 is only that the liquid metal in step (2) of Embodiment 3 is replaced with Ga ₈₀ In ₂₀ .

To sum up, the present invention provides a method for efficiently and conveniently preparing liquid metal nanoparticles by using amino acids, which solves the problems of low production scale and efficiency, large particle size and relatively poor biocompatibility of the existing liquid metal nanoparticles. Bad question. Different pH has a great influence on the dispersion effect of liquid metal nanoparticles, and the ratio of amino acid and liquid metal to solvent, different pH, grinding time, etc. can be flexibly adjusted to obtain liquid metal nanoparticles of different concentrations and particle sizes. The invention can realize simple and low-cost preparation of liquid metal nanoparticles, and broaden its application in the fields of bioengineering, drug delivery and release, flexible wear, printed circuits, heat dissipation of electronic products and the like.

The above-mentioned embodiments are only preferred embodiments for fully illustrating the present invention, and the protection scope of the present invention is not limited thereto. Equivalent substitutions or transformations made by those skilled in the art on the basis of the present invention are all within the protection scope of the present invention. The protection scope of the present invention is subject to the claims.

Claims (3)

1. a method utilizing amino acid to prepare liquid metal nanoparticles as ligand, is characterized in that, comprises the following steps: (1) Dissolve the amino acid in deionized water to obtain a clear amino acid aqueous solution; (2) adjusting the pH of the amino acid aqueous solution to 2-10; (3) Add liquid metal and zirconium beads dropwise to the pH-adjusted solution, and vibrate and grind to prepare liquid metal nanoparticles with a particle size of 100-1000 nm; Wherein, in step (1), the amino acid is cysteine, phenylalanine, lysine, histidine, tryptophan, aspartic acid, leucine, glycine, alanine, valine One or more of amino acid, isoleucine, proline, serine, tyrosine, methionine, asparagine, glutamine, threonine, glutamic acid and arginine; the amino acid The mass ratio to deionized water is (0.1～10):100; In step (3), the liquid metal is one or more of gallium, gallium-indium alloy, and gallium-indium-tin alloy; the mass ratio of the liquid metal to deionized water is (0.1-10): 100; the The diameter of the zirconium beads is one or more of 0.1 to 0.2mm, 0.3 to 0.4mm, 0.5 to 0.6mm, and 0.8 to 1mm; the ratio of the added amount of the zirconium beads to the mass ratio of the mixed solution is 10: (0.1 to 10 ); the vibration grinding time is 1-20h. 2 . The method for preparing liquid metal nanoparticles using amino acids as ligands according to claim 1 , wherein in step (1), the mass ratio of the amino acids to deionized water is 1:100. 3 . 3. Liquid metal nanoparticles prepared by the method according to claim 1 or 2.

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