A copper-nickel bimetallic doped carbonized polymer dot and preparation method thereof

Abstract

The present invention relates to a copper-nickel bimetallic doped carbonized polymer dot and a preparation method thereof. Disodium ethylenediaminetetraacetate and ethylenediamine are used as carbon sources, nickel chloride and cupric chloride are used as metal sources, and copper-nickel bimetallic coarsely doped carbonized polymer dots are obtained by microwave hydrothermal reaction. The obtained copper-nickel bimetallic coarsely doped carbonized polymer dots are subjected to centrifugation and dialysis for a period of time, and freeze-dried to obtain copper-nickel bimetallic doped carbonized polymer dot powder. The powder is redissolved in water to obtain a purified copper-nickel bimetallic doped carbonized polymer dot solution. The present invention achieves excellent free radical scavenging ability by exploring the inhibitory effect on superoxide free radicals and hydroxyl free radicals. The preparation method of the material is simple, the process is fast, and it is easy to implement.

Description

Technical Field

[0001] The invention relates to the technical field of new materials, and in particular to a method for preparing copper-nickel bimetallic doped carbonized polymer dots with the ability to scavenge free radicals. Background Art

[0002] The information disclosed in this background technology section is only intended to enhance the understanding of the overall background of the invention, and should not necessarily be regarded as an admission or any form of suggestion that the information constitutes the prior art already known to a person skilled in the art.

[0003] Free radicals are chemically reactive and play an important role in various processes, affecting most cellular functions, such as biomolecular distortion and cancer cell development. Excessive free radicals can disrupt normal cellular functions and promote damage to cellular components such as proteins, lipids, and DNA, leading to oxidative stress and pathobiological consequences such as inflammatory diseases and cancer. Therefore, scavenging excess free radicals is essential to maintain normal functions and extend the lifespan of materials and animals.

[0004] Carbonized polymer dots are an emerging class of 0-dimensional nanomaterials with particle sizes below 10 nm. They can be considered as cross-linked aggregates with a special carbon core and polymer shell structure, formed by dehydration, condensation, cross-linking and carbonization of organic small molecules and polymers with rich functional groups. Heteroatom doping is the most effective means to regulate the properties of carbonized polymer dots. Compared with most non-metallic heteroatoms, transition metals have unoccupied d orbitals and larger atomic radii. The electronic structure of carbonized polymer dots will be significantly adjusted with the presence of transition metal dopants. Doping carbonized polymer dots with transition metal atoms can endow them with new intrinsic properties and greatly expand their applications.

[0005] In recent years, carbon-based nanomaterials that can be used to scavenge free radicals have attracted extensive attention from researchers. However, the research findings on carbonized polymer dots with free radical scavenging ability are not sufficient, which also means that there is not enough room for their application. The research on metal-doped carbonized polymer dots needs to be further improved. Therefore, the preparation of a copper-nickel bimetallic doped carbonized polymer dot with free radical scavenging ability is particularly important for the research of carbonized polymer dots and their application in free radical scavenging. Summary of the invention

[0006] In view of the problems existing in the prior art, the purpose of the present invention is to provide a copper-nickel bimetallic doped carbonized polymer dot having the ability to scavenge free radicals and a preparation method thereof, wherein the copper-nickel bimetallic doped carbonized polymer dot has the ability to scavenge free radicals and excellent water solubility. Furthermore, the copper-nickel bimetallic doped carbonized polymer dot obtained by the present invention has the ability to scavenge superoxide free radicals and hydroxyl free radicals.

[0007] In order to achieve the above object, the technical solution of the present invention is as follows:

[0008] The present invention provides a method for preparing copper-nickel bimetallic doped carbonized polymer dots, comprising the following steps:

[0009] (1) After EDTA, nickel chloride and cupric chloride are dissolved in ultrapure water, EDTA is added to the solution and stirred until a clear solution is obtained.

[0010] (2) The solution in (1) is subjected to microwave hydrothermal reaction. After a period of reaction, the solution is centrifuged and filtered. After dialysis, the solution is freeze-dried and redissolved in ultrapure water to obtain copper-nickel bimetallic doped carbonized polymer dots.

[0011] The present invention also provides copper-nickel bimetallic doped carbonized polymer dots prepared by the above preparation method.

[0012] The present invention further provides the application of the copper-nickel bimetallic doped carbonized polymer dots in the field of biomedical materials, preferably in the application of scavenging free radicals.

[0013] The present invention has the following beneficial effects:

[0014] (1) The copper-nickel bimetallic carbonized polymer dots prepared by using disodium ethylenediaminetetraacetate and ethylenediamine as carbon sources and nickel chloride and cupric chloride as metal sources have excellent fluorescence intensity and abundant surface active groups, and can have a good inhibitory effect on free radicals.

[0015] (2) The copper-nickel bimetallic doped carbonized polymer dots prepared by the present invention overcome the difficulties of complex design ideas and cumbersome preparation processes of traditional multifunctional nanomaterials.

[0016] (3) The size of the copper-nickel bimetallic doped carbonized polymer dots prepared by the present invention is about 5 nm, and the carbonization degree of the above material can be adjusted by adjusting the amount of ethylenediamine and the microwave hydrothermal reaction time.

[0017] (4) The preparation process of the copper-nickel bimetallic doped carbonized polymer dots prepared by the present invention is simple and fast, and has relatively low requirements on instruments and equipment. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] The accompanying drawings constituting a part of the present invention are provided to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their description are used to explain the present invention and do not constitute improper limitations on the present invention.

[0019] Figure 1 This is a morphology of the copper-nickel bimetallic doped carbonized polymer dots prepared in Example 1 of the present invention.

[0020] Figure 2 This is the XRD pattern of the copper-nickel bimetallic doped carbonized polymer dots prepared in Example 1 of the present invention.

[0021] Figure 3 This is the XPS graph of the copper-nickel bimetallic doped carbonized polymer dots prepared in Example 1 of the present invention.

[0022] Figure 4 This is a graph showing the DPPH inhibition rate of the copper-nickel bimetallic doped carbonized polymer dots prepared in Example 1 of the present invention at different concentrations.

[0023] Figure 5 This is a graph of superoxide anion suppression rates of the copper-nickel bimetallic doped carbonized polymer dots prepared in Example 1 of the present invention at different concentrations (NBT method).

[0024] Figure 6 This is a graph of the hydroxyl radical inhibition rate of the copper-nickel bimetallic doped carbonized polymer dots prepared in Example 1 of the present invention at different concentrations (TMB method). DETAILED DESCRIPTION

[0025] It should be noted that the following detailed descriptions are all illustrative and intended to provide further explanation of the present invention. Unless otherwise specified, all technical and scientific terms used herein have the same meanings as those commonly understood by those skilled in the art to which the present invention belongs.

[0026] It should be noted that the terms used herein are only for describing specific embodiments and are not intended to limit the exemplary embodiments according to the present application. As used herein, unless the context clearly indicates otherwise, the singular form is also intended to include the plural form. In addition, it should be understood that when the terms "comprise" and / or "include" are used in this specification, it indicates the presence of features, steps, operations, devices, components and / or combinations thereof.

[0027] In one embodiment of the present invention, a method for preparing copper-nickel bimetallic doped carbonized polymer dots is provided, comprising the following steps:

[0028] (1) After ethylenediaminetetraacetic acid, nickel chloride and cupric chloride are dissolved in ultrapure water, ethylenediamine is added to the solution and dissolved and stirred until a clear solution is obtained;

[0029] (2) subjecting the solution in (1) to a microwave hydrothermal reaction, reacting for a period of time, centrifuging and filtering, dialysis, freeze-drying the solution, and redissolving it in ultrapure water to obtain copper-nickel bimetallic doped carbonized polymer dots;

[0030] Wherein, the amounts of ethylenediaminetetraacetic acid, nickel chloride and cupric chloride are 1 mmol, 0.4-0.6 mmol, 0.4-0.6 mmol respectively;

[0031] The microwave hydrothermal reaction conditions are 350W-630W power for 10-20min.

[0032] In some embodiments, the amounts of disodium ethylenediaminetetraacetate, nickel chloride and cupric chloride used in step (1) are 1 mmol, 0.5 mmol, and 0.5 mmol, respectively, which are dissolved in 15 ml of ultrapure water.

[0033] In some embodiments, the microwave hydrothermal reaction condition in step (1) is to react at a power of 500 W for 15 min.

[0034] In some embodiments, the amount of ethylenediamine added in step (1) is 0.15 mmol.

[0035] In some embodiments, the speed of high-speed centrifugation in step (2) is 11000 rpm, the centrifugation time is 10 min, and the centrifugation operation is repeated 3 times.

[0036] In some embodiments, the filter head specification used for filtration in step (2) is 0.22 microns.

[0037] In some embodiments, in step (2), the dialysis bag has a molecular weight cutoff of 1000 Da and the dialysis time is 24 h.

[0038] The copper-nickel bimetallic doped carbonized polymer dots prepared by using disodium ethylenediaminetetraacetate and ethylenediamine as carbon sources and nickel chloride and cupric chloride as metal sources have excellent fluorescence intensity and abundant surface active groups, and can have a good inhibitory effect on free radicals.

[0039] The copper-nickel bimetallic doped carbonized polymer dots prepared by the present invention overcome the difficulties of complex design ideas and cumbersome preparation processes of traditional multifunctional nanomaterials.

[0040] The size of the copper-nickel bimetallic doped carbonized polymer dots prepared by the present invention is about 5 nm, and the carbonization degree of the above material can be adjusted by regulating the amount of ethylenediamine and the microwave hydrothermal reaction time.

[0041] The preparation process of the copper-nickel bimetallic doped carbonized polymer dots prepared by the present invention is simple and rapid, and has relatively small requirements on instruments and equipment.

[0042] The present invention will be further explained and illustrated below in conjunction with specific embodiments.

[0043] Example 1

[0044] A method for preparing copper-nickel bimetallic doped carbonized polymer dots with free radical scavenging ability comprises the following steps:

[0045] 1 mmol of disodium ethylenediaminetetraacetate, 0.5 mmol of nickel chloride and 0.5 mmol of cupric chloride were weighed and dissolved in 15 ml of ultrapure water. 0.15 mmol of ethylenediamine was added to the solution, and stirring was continued for 15 min until the solution was clear. A polytetrafluoroethylene reactor liner was added, and the reactor was completely sealed and checked for airtightness. The reactor was reacted at a microwave power of 500 W for 15 min. When the reactor temperature was completely reduced to room temperature, the reactor was centrifuged at 10000 rpm for 10 min to remove impurities generated during the reaction. The centrifugation operation was repeated 3 times, and then the solution was filtered with a 0.22 micron filter. The crude copper-nickel bimetallic doped carbonized polymer dots were then dialyzed for 24 hours with a dialysis bag with a molecular weight cutoff of 1000 Da to remove impurity ions in the solution. The dialyzed copper-nickel bimetallic doped carbonized polymer dots solution was freeze-dried and then redissolved in ultrapure water to obtain purified copper-nickel bimetallic doped carbonized polymer dots.

[0046] Figure 1 The figure shows the transmission electron micrograph of the copper-nickel bimetallic doped carbonized polymer dots prepared in Example 1. It can be seen that the size of the copper-nickel bimetallic doped carbonized polymer dots is about 3-7 nm. Figure 2 This is the XRD pattern of copper-nickel bimetallic doped carbonized polymer dots. It can be seen from the figure that the amorphous peak in the XRD can confirm the successful synthesis of copper-nickel bimetallic doped carbonized polymer dots. Figure 3 This is the XPS spectrum of copper-nickel bimetallic doped carbonized polymer dots. It can be seen from the figure that there are very rich functional groups on the material, which indirectly confirms the successful synthesis of copper-nickel bimetallic doped carbonized polymer dots.

[0047] The copper-nickel bimetallic carbonized polymer dots prepared in Example 1 were used as the test object to test the material's ability to inhibit free radicals. Figure 4 The figure shows the ability of copper-nickel bimetallic doped carbonized polymer dots to inhibit DPPH. The capture capacity of copper-nickel bimetallic doped carbonized polymer dots for DPPH has been maintained at around 30-40%. Figure 5 The figure shows the ability of copper-nickel bimetallic doped carbonized polymer dots to inhibit superoxide radicals. Copper-nickel bimetallic doped carbonized polymer dots showed high efficiency in capturing superoxide anions. When the material concentration was 200 μg / ml, the capture rate of superoxide anions reached 85%. Figure 6 The figure shows the ability of copper-nickel bimetallic doped carbonized polymer dots to inhibit hydroxyl radicals. Copper-nickel bimetallic doped carbonized polymer dots also have good capture ability for hydroxyl radicals, and when the material concentration is 2 mg / ml, the capture ability for hydroxyl radicals is as high as 92%.

[0048] Example 2

[0049] A method for preparing copper-nickel bimetallic doped carbonized polymer dots with free radical scavenging ability comprises the following steps:

[0050] 1 mmol of disodium ethylenediaminetetraacetate, 0.5 mmol of nickel chloride and 0.5 mmol of cupric chloride were weighed and dissolved in 15 ml of ultrapure water. 0.15 mmol of ethylenediamine was added to the solution, and stirring was continued for 15 min until the solution was clear. A polytetrafluoroethylene reactor liner was added, and the reactor was completely sealed and checked for airtightness. The reactor was reacted at a microwave power of 630 W for 10 min. When the reactor temperature was completely reduced to room temperature, the reactor was centrifuged at 10000 rpm for 10 min to remove impurities generated during the reaction. The centrifugation operation was repeated 3 times, and then the solution was filtered with a 0.22 micron filter. The crude copper-nickel bimetallic doped carbonized polymer dots were then dialyzed for 24 hours with a dialysis bag with a molecular weight cutoff of 1000 Da to remove impurity ions in the solution. The dialyzed copper-nickel bimetallic doped carbonized polymer dots solution was freeze-dried and then redissolved in ultrapure water to obtain purified copper-nickel bimetallic doped carbonized polymer dots.

[0051] Example 3

[0052] A method for preparing copper-nickel bimetallic doped carbonized polymer dots with free radical scavenging ability comprises the following steps:

[0053] 1 mmol of disodium ethylenediaminetetraacetate, 0.5 mmol of nickel chloride and 0.5 mmol of cupric chloride were weighed and dissolved in 15 ml of ultrapure water. 0.15 mmol of ethylenediamine was added to the solution, and stirring was continued for 15 min until the solution was clear. A polytetrafluoroethylene reactor liner was added, and the reactor was completely sealed and checked for airtightness. The reactor was reacted at a microwave power of 350 W for 20 min. When the reactor temperature was completely reduced to room temperature, the reactor was centrifuged at 10000 rpm for 10 min to remove impurities generated during the reaction. The centrifugation operation was repeated 3 times, and then the solution was filtered with a 0.22 micron filter. The crude copper-nickel bimetallic doped carbonized polymer dots were then dialyzed for 24 hours with a dialysis bag with a molecular weight cutoff of 1000 Da to remove impurity ions in the solution. The dialyzed copper-nickel bimetallic doped carbonized polymer dots solution was freeze-dried and then redissolved in ultrapure water to obtain purified copper-nickel bimetallic doped carbonized polymer dots.

[0054] Finally, it should be noted that the above is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments or replace some of them with equivalents. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for preparing copper-nickel bimetallic doped carbonized polymer dots, characterized in that: The steps include: (1) After dissolving disodium ethylenediaminetetraacetate, nickel chloride and cupric chloride in ultrapure water, add ethylenediamine to the solution and stir until a clear solution is obtained; (2) subjecting the solution in (1) to a microwave hydrothermal reaction, and after a period of reaction, centrifugally filtering and dialysis, freeze-drying the solution, and redissolving it in ultrapure water to obtain copper-nickel bimetallic doped carbonized polymer dots; Wherein, the dosage of disodium ethylenediaminetetraacetate, nickel chloride and cupric chloride is 1 mmol, 0.4-0.6 mmol, 0.4-0.6 mmol respectively; The microwave hydrothermal reaction conditions are 350W-630W power for 10-20min; The amount of ethylenediamine added in step (1) is 0.15 mmol; In step (2), the speed of high-speed centrifugation is 11000 rpm, the centrifugation time is 10 min, and the centrifugation operation is repeated 3 times; In step (2), the molecular weight cutoff of the dialysis bag is 1000 Da, and the dialysis time is 24 h.

2. The preparation method according to claim 1, characterized in that: In step (1), the amounts of disodium ethylenediaminetetraacetate, nickel chloride and cupric chloride used are 1 mmol, 0.5 mmol and 0.5 mmol respectively.

3. The preparation method according to claim 1, characterized in that: In step (1), disodium ethylenediaminetetraacetate, nickel chloride and cupric chloride are dissolved in 15 ml of ultrapure water.

4. The preparation method according to claim 1, characterized in that: The microwave hydrothermal reaction condition in step (1) is to react at a power of 500 W for 15 min.

5. The preparation method according to claim 1, characterized in that: The filter head specification used for filtration in step (2) is 0.22 microns.

6. Copper-nickel bimetallic doped carbonized polymer dots prepared according to the preparation method described in any one of claims 1 to 5 above.

7. Use of the copper-nickel bimetallic doped carbonized polymer dots according to claim 6 in the preparation of biomedical materials for scavenging free radicals.

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