Preparation method of copper sulfide nanomaterial

Abstract

The application discloses a preparation method of copper sulfide nanomaterial. The method comprises the following steps: dissolving sodium polyacrylate in deionized water, stirring for 20-30 min, and adding isopropyl alcohol dropwise to obtain a sodium polyacrylate ball solution; then adding a copper salt solution to the sodium polyacrylate ball solution, and obtaining PAAS / Cu(OH)2 NPs after reaction; dispersing the PAAS / Cu(OH)2 NPs in deionized water, adding a sulfur source, and reacting in a constant-temperature water bath at 60-80 DEG C under stirring for 30-60 min to obtain copper sulfide nanomaterial; and the sulfur source is sodium thiosulfate or thioacetamide. The application has the advantages of mild reaction condition, fast preparation, uniform particle size, beautiful appearance, good photothermal stability and the like.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of copper sulfide nanomaterials, and particularly relates to a preparation method of copper sulfide nanomaterials. BACKGROUND

[0002] Bacterial infection is an acute systemic infection caused by pathogenic bacteria or conditional pathogenic bacteria invading the blood circulation to grow and reproduce, producing toxins and other metabolites. Clinically, antibiotics are mainly used for treatment. However, the overuse of antibiotics has resulted in drug resistance in many bacteria. Therefore, there is an urgent need to find effective alternative strategies to combat drug-resistant bacteria. In recent years, with the development of nanotechnology, nanomaterials have attracted more and more attention from researchers in various fields.

[0003] Copper sulfide is an inorganic compound, which is a sulfide of divalent copper with the chemical formula CuS and is black-brown. In addition to these basic advantages such as low cost and good biocompatibility, it has strong and wide absorption in the near-infrared region, making it have the potential of a photoresponsive nanocatalyst. In addition, copper-based materials mediated Fenton reaction can also be applied to antibiosis, so it has become the focus of many scholars.

[0004] There are many methods for synthesizing copper sulfide nanomaterials, such as hydrothermal method, wet chemical synthesis method, microwave method, etc. Taking the most classic hydrothermal method as an example, the hydrothermal method uses a high-pressure hydrothermal reactor, the reaction time is long, the synthesis process is complex, the cost is high, it is not easy to control, and the synthesized nanomaterials have uneven particle size and poor stability. Therefore, it is necessary to develop a kind of copper sulfide nanosphere material which can be quickly prepared, has uniform particle size, beautiful appearance, good photothermal stability and chemical power. SUMMARY

[0005] The present application aims to solve the problems of complex synthesis process, uneven nanometer particle size, poor stability, and high cost in the prior art. A preparation method of copper sulfide nanomaterials is provided. The method uses a template method to first prepare a sodium polyacrylate ball template, then adds copper salt, and then adds thioacetamide or sodium thiosulfate in a 60-80℃ water bath, to form relatively uniform spherical nanoparticles on the sodium polyacrylate ball template. The present application has the advantages of mild reaction conditions, fast preparation, uniform particle size, beautiful appearance, and good photothermal stability.

[0006] The technical scheme of the present application is as follows:

[0007] A preparation method of copper sulfide nanomaterials, the method comprising the following steps:

[0008] Step one, dissolve sodium polyacrylate in deionized water, stir for 20-30 minutes, and add isopropyl alcohol dropwise to obtain a sodium polyacrylate ball solution;

[0009] The mass ratio of the sodium polyacrylate to the isopropyl alcohol is 1:(320-470).

[0010] Step two: the copper salt is completely dissolved in water, and then added into the sodium polyacrylate ball solution obtained in step one, and stirred immediately to mix uniformly, the reaction time is 12-15 hours, a blue solution is obtained, and then centrifuged and washed with deionized water to obtain PAAS / Cu(OH)2 NPs;

[0011] The mass ratio of the sodium polyacrylate to the copper salt is 1:(0.5-6).

[0012] Step three: the PAAS / Cu(OH)2 NPs obtained in step two are dispersed in deionized water, and a sulfur source is added, and then reacted in a constant temperature water bath at 60-80°C for 30-60 minutes to obtain copper sulfide nanomaterials.

[0013] The molar ratio of the copper salt to the sulfur source is 100:(1-10).

[0014] Further, step four: the solution containing the copper sulfide nanomaterials obtained in step three is centrifuged, washed and dried.

[0015] In step one, the volume ratio of the deionized water to the isopropyl alcohol is 1:(4-8).

[0016] In step two, the copper salt is one of copper nitrate, copper chloride or copper sulfate.

[0017] In step three, the sulfur source is sodium thiosulfate or thioacetamide.

[0018] Further, the prepared copper sulfide nanomaterials are spherical, and the particle size is about 345-355 nm.

[0019] The present application has the following advantages:

[0020] The present application uses a template method to synthesize copper sulfide nanoparticles on a sodium polyacrylate ball template. The sodium polyacrylate ball is negatively charged, and the copper salt is positively charged, and the two are combined through electrostatic adsorption, and a sulfur source is added for sulfidation. The synthesized nanoparticle material has uniform particle size and spherical morphology. Since the copper ions can be coordinated with the carboxyl groups on the sodium polyacrylate ball, the copper ion coordination compound formed by this coordination can still provide a stable chemical site, so that the copper ions and the sulfur dianion continue to react to form copper sulfide nanoparticles. After the copper sulfide nanoparticles are continuously subjected to four cycles of near-infrared laser on / off irradiation, the temperature rise does not change significantly, indicating that the product has good stability. The synthesized copper sulfide nanoparticles are used for methylene blue degradation experiments, and the absorbance value at 665 nm gradually decreases with time, indicating that the product has methylene blue degradation ability. The reaction conditions of the present application are mild, simple and easy to control, and the reaction time is short. Attached Figure Description

[0021] Figure 1 The image shows a scanned electron microscope (SEM) image of the copper sulfide nanomaterials obtained in Example 3. Figure 1 a represents PAAS / Cu(OH)2NPs. Figure 1 b represents CuS NPs;

[0022] Figure 2 The graph shows the temperature changes of the copper sulfide nanoparticles obtained in Example 3 during four switching cycles. Figure 2 a represents the light intensity under 808nm near-infrared illumination. Figure 2 b represents the illumination under 1064nm near-infrared light;

[0023] Figure 3 This is a diagram showing the methylene blue degradation of the copper sulfide nanomaterials obtained in Example 3. Detailed Implementation

[0024] The technical solutions will now be clearly and completely described in conjunction with embodiments of the present invention. Obviously, the described embodiments are merely some, not all, of the embodiments of the present invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0025] This invention provides a method for preparing copper sulfide nanomaterials, the method comprising:

[0026] Step 1: Dissolve sodium polyacrylate in deionized water, stir for 20-30 minutes, and add isopropanol dropwise to obtain a sodium polyacrylate ball solution. The mass ratio of sodium polyacrylate to isopropanol is 1:(320-470); the volume ratio of added deionized water to isopropanol is 1:(4-8).

[0027] Step 2: Dissolve the copper salt completely in water, then add it to the 10 ml sodium polyacrylate ball solution obtained in Step 1. Stir and mix thoroughly immediately. The reaction time is 12-13 hours to obtain a blue solution. Centrifuge the solution and wash it several times with deionized water. The copper salt is one of copper nitrate, copper chloride, or copper sulfate, and the mass ratio of sodium polyacrylate to copper salt is 1:(0.5-6).

[0028] Step 3: Redisperse the product obtained in Step 2 in deionized water, place it in a constant temperature water bath, heat and stir, and add a sulfur source to obtain a dark green solution; the sulfur source is sodium thiosulfate or thioacetamide, and the molar ratio of copper salt to sulfur source is 100:(1-10). The temperature of the water bath is 60-80℃, and the reaction time is 30-60 min.

[0029] Step four: the ink green solution obtained in step three is treated by centrifugation, washing and drying to obtain the copper sulfide nanomaterial; the drying time is not less than 5 h, and the drying temperature is 60°C.

[0030] The method mainly controls the small crystal particle size and high uniformity of the prepared nanometer copper sulfide through the "two-step method" of steps two and three under relatively mild reaction conditions. The temperature selected in the application is mild and easy to achieve. The prepared nanometer copper sulfide is spherical, and the particle size is about 345-355 nm. Due to the large specific surface area, it can load other traditional chemotherapeutic drugs, and is used for realizing three-mode antibiosis, and can become an effective new antibacterial nanometer platform.

[0031] Example 1

[0032] Dissolve 0.1 g of sodium polyacrylate in 10 ml of deionized water, stir for 25 min, and add 50 ml of isopropyl alcohol to obtain a sodium polyacrylate ball solution; 0.08 g (0.5 mmol) of copper sulfate is completely dissolved in 300 ul of water, added to 10 ml of the obtained sodium polyacrylate ball solution, and stirred to obtain a blue solution. The reaction time is 12 h. It is centrifuged and washed with deionized water several times to obtain PAAS / Cu(OH)2NPs; the obtained product is redispersed in 10 ml of deionized water, placed in a 70°C constant temperature water bath, stirred and added with 0.009 g (0.057 mmol) of sodium thiosulfate, and the reaction time is 40 min. An ink green solution is obtained. The obtained ink green solution is treated by centrifugation, washing and drying to obtain the copper sulfide nanomaterial; the drying time is 6 h, and the drying temperature is 60°C.

[0033] Example 2

[0034] Dissolve 0.1 g of sodium polyacrylate in 10 ml of deionized water, stir for 30 min, and add 60 ml of isopropyl alcohol to obtain a sodium polyacrylate ball solution. 0.08 g (0.6 mmol) of copper chloride is completely dissolved in 300 ul of water, added to 10 ml of the obtained sodium polyacrylate ball solution, and stirred to obtain a blue solution. The reaction time is 13 h. It is centrifuged and washed with deionized water several times to obtain PAAS / Cu(OH)2NPs; the obtained product is redispersed in 10 ml of deionized water, placed in a 65°C constant temperature water bath, stirred and added with 0.01 g (0.063 mmol) of sodium thiosulfate, and the reaction time is 40 min. An ink green solution is obtained. The obtained ink green solution is treated by centrifugation, washing and drying to obtain the copper sulfide nanomaterial; the drying time is 6 h, and the drying temperature is 60°C.

[0035] Example 3

[0036] Dissolve 0.1 g of sodium polyacrylate in 10 ml of deionized water, stir for 30 min, and add 40 ml of isopropyl alcohol to it to obtain a sodium polyacrylate ball solution. Dissolve 0.08 g (i.e. 0.6 mmol) of copper chloride completely in 300 ul of water, add 10 ml of the obtained sodium polyacrylate ball solution, stir to mix uniformly to obtain a blue solution, and react for 12 h. Centrifuge and wash with deionized water several times to obtain PAAS / Cu(OH)2NPs. Redisperse the obtained product in 10 ml of deionized water, place in a 60°C constant temperature water bath, stir and add 0.006 g (i.e. 0.008 mmol) of thioacetamide, and react for 30 min. Obtain a dark green solution. Centrifuge, wash and dry the obtained dark green solution to obtain a copper sulfide nanomaterial; the drying time is 6 h and the drying temperature is 60°C.

[0037] Example 4

[0038] Dissolve 0.1 g of sodium polyacrylate in 10 ml of deionized water, stir for 30 min, and add 50 ml of isopropyl alcohol to it to obtain a sodium polyacrylate ball solution. Dissolve 0.08 g (i.e. 0.4 mmol) of copper nitrate completely in 300 ul of water, add 10 ml of the obtained sodium polyacrylate ball solution, stir to mix uniformly to obtain a blue solution, and react for 12 h. Centrifuge and wash with deionized water several times to obtain PAAS / Cu(OH)2NPs. Redisperse the obtained product in 10 ml of deionized water, place in a 60°C constant temperature water bath, stir and add 0.007 g (i.e. 0.009 mmol) of thioacetamide, and react for 30 min. Obtain a dark green solution. Centrifuge, wash and dry the obtained dark green solution to obtain a copper sulfide nanomaterial; the drying time is 6 h and the drying temperature is 60°C.

[0039] Performance verification and testing are as follows:

[0040] Stability test

[0041] Take 200 μL of 200 μg mL-1 product of Example 3, place in a 2 ml centrifuge tube, use an LSR-PS-II type laser 808 nm near infrared at a distance of 20-25 cm from the centrifuge tube to irradiate the centrifuge tube, the laser power is 1 W / cm 2 , irradiate for 5 min, naturally cool for 5 min, under this condition, the photothermal stability of the product is determined by 4 cycles of laser on / off.

[0042] The results are shown in Figure 2 , after continuous near-infrared laser on / off irradiation for 4 cycles, the temperature rise amplitude does not change significantly, indicating that the product has good stability.

[0043] Methylene blue degradation test

[0044] The product of column 3 (1 mL, 1 mg mL -1 ) was incubated with 300 μL of 100 mM GSH for 15 min, then 30 μL of 100 mM H2O2, 50 μL of 0.1 mg mL -1 MB, 620 μL of PBS were added, and after centrifugation, the absorbance of MB at 665 nm was detected at different times by ultraviolet-visible spectrophotometry.

[0045] The results are shown in Table 1, and the absorbance value at 665 nm gradually decreased over time, indicating that the product had methylene blue degradation ability. Figure 3

[0046] The embodiment of the present application has the following beneficial effects: the preparation method of the copper sulfide nanomaterial is mild, simple and controllable, and the prepared copper sulfide nanomaterial has strong stability.

[0047] The above only describes the preferred embodiments of the present application and is not intended to limit the present application, and any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

[0048] The details of the present application are known technology.​

Claims

1. A method for preparing copper sulfide nanomaterials, characterized in that the method includes the following steps: Step 1: Dissolve sodium polyacrylate in deionized water, stir for 20-30 minutes, and add isopropanol dropwise to obtain a sodium polyacrylate ball solution. in, The mass ratio of sodium polyacrylate to isopropanol is 1:(320~470). Step 2: Dissolve the copper salt completely in water, then add it to the sodium polyacrylate ball solution obtained in Step 1. Stir and mix thoroughly immediately. The reaction time is 12-15 hours. A blue solution is obtained. Centrifuge the solution and wash it with deionized water to obtain PAAS / Cu(OH)2 NPs. The mass ratio of sodium polyacrylate to copper salt is 1:(0.5~6). Step 3: Disperse the PAAS / Cu(OH)2 NPs obtained in Step 2 in deionized water, add sulfur source, and react in a constant temperature water bath at 60~80℃ with stirring for 30min~60min to obtain copper sulfide nanomaterials; The molar ratio of copper salt to sulfur source is 100:(1~10).

2. The method for preparing copper sulfide nanomaterials as described in claim 1, characterized in that it further includes step four: centrifuging, washing and drying the solution containing copper sulfide nanomaterials obtained in step three.

3. The method for preparing copper sulfide nanomaterials as described in claim 1, characterized in that in step one, the volume ratio of deionized water to isopropanol is 1:(4~8).

4. The method for preparing copper sulfide nanomaterials as described in claim 1, characterized in that: In step two, the copper salt is one of copper nitrate, copper chloride, or copper sulfate.

5. The method for preparing copper sulfide nanomaterials as described in claim 1, characterized in that: In step three, the sulfur source is sodium thiosulfate or thioacetamide.

6. The method for preparing copper sulfide nanomaterials as described in claim 1, characterized in that the obtained copper sulfide nanomaterials are spherical with a particle size of 345~355 nm.

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