CN111570820B - Preparation method and application of copper nanocluster - Google Patents

Preparation method and application of copper nanocluster Download PDF

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CN111570820B
CN111570820B CN202010315943.9A CN202010315943A CN111570820B CN 111570820 B CN111570820 B CN 111570820B CN 202010315943 A CN202010315943 A CN 202010315943A CN 111570820 B CN111570820 B CN 111570820B
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copper
glutathione
crude product
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nanoclusters
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CN111570820A (en
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常柏松
孙涛垒
安宇
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Wuhan University of Technology WUT
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
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    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

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Abstract

The invention discloses a preparation method of copper nanoclusters, which comprises the following steps: mixing a copper source aqueous solution and a glutathione aqueous solution, and stirring at normal temperature to obtain milky hydrogel; heating the milky hydrogel to 75-85 ℃, and preserving heat for 10-20 min to obtain a reaction product; dropwise adding NaOH solution into the reaction product until the reaction product is clear and transparent to obtain a crude product; cooling the crude product to normal temperature, and purifying and separating to obtain copper nanoclusters; wherein the molar ratio of the copper source to the glutathione is 1: 1 to 5. The method has the advantages of mild synthesis conditions, low cost, simple and controllable operation, easy repetition and amplification, suitability for mass production, no other reducing agent involved in the synthesis process, and avoidance of influence on the application of the product. The invention also provides application of the copper nanocluster in removing superoxide anion radicals in cigarettes.

Description

Preparation method and application of copper nanocluster
Technical Field
The invention belongs to the technical field of nano synthesis, and particularly relates to a preparation method and application of a copper nanocluster.
Background
The metal nanocluster, which is an ultra-small nanoparticle having a metal core size of about 2nm, closes a gap between an organometallic compound and a crystalline metal nanoparticle, and is generally composed of several to several tens of metal atoms. One of the obvious features of the metal nanocluster is its strong photoluminescence, and has good light stability, large stokes shift, and its size is close to the fermi wavelength of electrons, which characteristics make the metal nanocluster exhibit interesting physical and chemical characteristics, thus attracting extensive interest of researchers. Copper is cheaper than gold and silver. Therefore, the copper nanoclusters gradually become an important component in the metal nanomaterials and are widely applied to the research fields of chemical analysis, biosensing, biological imaging, ion detection and the like.
Cigarette smoke contains high concentrations of toxic free radicals (> 10 per puff)16Molecule) includes active oxygen and active nitrogen. Oxidative damage from exposure to these free radicals can lead to cancer, cardiovascular disease, and chronic pulmonary disease, among others. Currently, the use of antioxidants such as glutathione, vitamins a, C and E, tea polyphenols or superoxide dismutase preparations to reduce free radical damage to the oropharynx and respiratory tract has been limited by their temperature stability in cigarettes and other tobacco products.
The existing preparation method of the copper nanocluster is complicated and is not suitable for large-scale synthesis, and other reducing agents are used in part of the synthesis method, so that the subsequent application is not facilitated.
Disclosure of Invention
The invention aims to overcome the technical defects and provides a preparation method of a copper nanocluster, which is simple and suitable for large-scale synthesis, does not involve other reducing agents in the preparation process, and does not influence the subsequent application of the copper nanocluster; another object of the present invention is to provide a method for removing superoxide anion radicals in cigarettes, which comprises the step of removing superoxide anion radicals from cigarettes.
In order to achieve the technical purpose, the technical scheme of the invention provides a preparation method of copper nanoclusters, which comprises the following steps: mixing a copper source aqueous solution and a glutathione aqueous solution, and stirring at normal temperature to obtain milky hydrogel; heating the milky hydrogel to 75-85 ℃, and preserving heat for 10-20 min to obtain a reaction product; dropwise adding NaOH solution into the reaction product until the reaction product is clear and transparent to obtain a crude product; cooling the crude product to normal temperature, and purifying and separating to obtain copper nanoclusters; wherein the molar ratio of the copper source to the glutathione is 1: 1 to 5.
The technical scheme of the invention also provides the application of the copper nanocluster in removing superoxide anion radicals in cigarettes.
Compared with the prior art, the invention has the beneficial effects that:
1. the preparation method of the copper nanocluster provided by the invention has the advantages of mild synthesis conditions, low cost, simple and controllable operation, easy repetition and amplification, suitability for mass production, no other reducing agent involved in the synthesis process, and avoidance of influence on the application of the product;
2. the copper nanocluster prepared by the method is small in size, large in specific surface area, strong in light stability, small in toxic and side effects and good in water solubility, and provides a wide prospect for subsequent application;
3. the copper nanocluster prepared by the method can effectively remove superoxide anion free radicals in cigarette smoke, and when the copper nanocluster is applied to cigarettes, the harm of tobacco to bodies is reduced.
Drawings
FIG. 1 is a fluorescence emission spectrum of the copper nanoclusters prepared in examples 1 to 5, wherein the excitation wavelength is 365nm and the maximum emission wavelength is 590 nm;
fig. 2 is a transmission electron micrograph of the copper nanoclusters prepared in example 4;
fig. 3 is an infrared spectrum of the copper nanoclusters prepared in example 4;
fig. 4 is an XPS spectrum of the copper nanoclusters prepared in example 4;
FIG. 5 is a graph showing the SOD inhibitory effect of the copper nanoclusters prepared in example 4;
FIG. 6 is a graph showing the effect of removing superoxide anion radicals from cigarette smoke by the copper nanoclusters prepared in example 4;
fig. 7 is a graph showing the effect of the cytotoxicity test on the copper nanoclusters manufactured in example 4.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a preparation method of copper nanoclusters, which comprises the following steps:
mixing a copper source aqueous solution and a glutathione aqueous solution, and stirring at normal temperature to obtain milky hydrogel; heating the milky hydrogel to 75-85 ℃, and preserving heat for 10-20 min to obtain a reaction product; dropwise adding NaOH solution into the reaction product until the reaction product is clear and transparent to obtain a crude product, cooling the crude product to normal temperature, and purifying and separating to obtain copper nanoclusters (GSH @ CuNCs for short); wherein the molar ratio of the copper source to the glutathione is 1: 1 to 5.
In some preferred embodiments of the present invention, the copper source is any one of copper sulfate, copper nitrate, and copper chloride.
In some preferred embodiments of the invention, the glutathione is reduced glutathione such that Cu is converted to Cu2+Reducing and avoiding using other reducing agents to influence the final product.
In some preferred embodiments of the invention, the molar ratio of copper source to glutathione is 1: 4.
in some preferred embodiments of the present invention, the concentration of the NaOH solution is 2 to 3 mol/L.
In some preferred embodiments of the invention, the milky white hydrogel is heated to 80 ℃ and incubated for 15 min.
In the invention, the ethanol solution is used for purifying and separating the crude product, and the following method is specifically adopted: adding an ethanol solution into the crude product, aggregating and precipitating, and then centrifugally separating the mixed solution; the volume ratio of the ethanol solution to the crude product is 4-5: 1, the concentration of the ethanol solution is 95%.
The embodiment of the invention also provides application of the copper nanocluster in removing superoxide anion radicals in cigarettes.
The copper nanocluster is applied to removing superoxide anion free radicals in cigarettes, and the method specifically comprises the following steps:
preparing a copper nanocluster aqueous solution, soaking a cigarette filter tip into the copper nanocluster aqueous solution at normal temperature for 20-40 min, igniting the cigarette and blowing air into the cigarette filter tip to enable smoke to pass through the cigarette filter tip, and detecting superoxide anion free radicals in the smoke by taking iodonitrotetrazole violet (INT for short) as an indicator through ultraviolet spectrum.
In some preferred embodiments of the present invention, the concentration of the copper nanocluster aqueous solution is 60 to 180 mg/L.
In some preferred embodiments of the invention, the cigarette filter is aerated, and the flow rate of gas in the cigarette filter is kept to be 80-120 mL/min.
In some preferred embodiments of the invention, the ultraviolet spectrum detection is carried out by detecting the ultraviolet spectrum absorption intensity of the iodonitrotetrazole violet at 505nm after the smoke is introduced, so as to judge the scavenging degree of superoxide anion free radicals in the cigarette; if the removal degree is higher, the ultraviolet absorption value of the iodine nitrotetrazole violet at 505nm after the smoke is introduced is lower; if the removal degree is lower, the ultraviolet absorption value of the iodonitrotetrazole violet at 505nm after the smoke is introduced is higher.
In some preferred embodiments of the invention, the concentration of iodonitrotetrazole violet is 1.5 mmol/L.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The experimental methods in the present invention are conventional methods unless otherwise specified. The experimental materials used in the present invention were all purchased from the market unless otherwise specified.
Example 1:
embodiment 1 of the present invention provides a method for preparing a copper nanocluster, including the steps of:
dissolving 0.625g reduced glutathione in 100mL ultrapure water at room temperature to obtain glutathione aqueous solution, and dropwise adding 4mL of 0.5mol/L Cu (NO) into the glutathione aqueous solution under vigorous stirring3)2After the solution is added, stirring the mixed solution at normal temperature until the color of the mixed solution fades and a milky hydrogel is gradually formed; heating the milky hydrogel from room temperature until no milky hydrogel is generatedHeating to 80 ℃, keeping the temperature at 80 ℃ for 15min, and dropwise adding 3mol/L NaOH solution into the reaction product until the reaction product is clear and transparent to obtain a crude product; the crude product was transferred to a rotary evaporator and rotary evaporated to 20mL at 70 ℃. And adding ethanol solution with the volume 5 times that of the crude product after rotary evaporation, after aggregation and precipitation, centrifuging at the rotating speed of 8000rpm for 30min to obtain a product, repeating the step for three times, and freeze-drying the finally obtained product in a freeze dryer to obtain the solid copper nanocluster.
Example 2:
embodiment 2 of the present invention provides a method for preparing a copper nanocluster, including the steps of:
dissolving 1.25g reduced glutathione in 100mL ultrapure water at room temperature to obtain glutathione aqueous solution, and dropwise adding 4mL of 0.5mol/L Cu (NO) into the glutathione aqueous solution under vigorous stirring3)2After the solution is added, stirring the mixed solution at normal temperature until the color of the mixed solution fades and a milky hydrogel is gradually formed; when the milky-white hydrogel is not generated any more, heating the milky-white hydrogel to 75 ℃ from the normal temperature, preserving the heat at 75 ℃ for 20min, and dropwise adding 3mol/L NaOH solution into the reaction product until the reaction product is clear and transparent to obtain a crude product; the crude product was transferred to a rotary evaporator and rotary evaporated to 20mL at 70 ℃. And adding ethanol solution with the volume 5 times that of the crude product after rotary evaporation, after aggregation and precipitation, centrifuging at the rotating speed of 8000rpm for 30min to obtain a product, repeating the step for three times, and freeze-drying the finally obtained product in a freeze dryer to obtain the solid copper nanocluster.
Example 3:
embodiment 3 of the present invention provides a method for preparing a copper nanocluster, including the steps of:
dissolving 1.875g of reduced glutathione in 100mL of ultrapure water at room temperature to obtain a glutathione aqueous solution, and dropwise adding 4mL of 0.5mol/L Cu (NO) into the glutathione aqueous solution under vigorous stirring3)2Adding the solution, and stirring the mixed solution at normal temperature until the color of the mixed solution fadesGradually forming milky hydrogel; when the milky-white hydrogel is not generated any more, heating the milky-white hydrogel to 85 ℃ from the normal temperature, preserving the heat at 85 ℃ for 10min, and dropwise adding 3mol/L NaOH solution into the reaction product until the reaction product is clear and transparent to obtain a crude product; the crude product was transferred to a rotary evaporator and rotary evaporated to 20mL at 70 ℃. And adding ethanol solution with the volume 5 times that of the crude product after rotary evaporation, after aggregation and precipitation, centrifuging at the rotating speed of 8000rpm for 30min to obtain a product, repeating the step for three times, and freeze-drying the finally obtained product in a freeze dryer to obtain the solid copper nanocluster.
Example 4:
embodiment 4 of the present invention provides a method for preparing a copper nanocluster, including the steps of:
dissolving 2.5g reduced glutathione in 100mL ultrapure water at room temperature to obtain glutathione aqueous solution, and dropwise adding 4mL of 0.5mol/L Cu (NO) into the glutathione aqueous solution under vigorous stirring3)2After the solution is added, stirring the mixed solution at normal temperature until the color of the mixed solution fades and a milky hydrogel is gradually formed; when the milky-white hydrogel is not generated any more, heating the milky-white hydrogel to 80 ℃ from the normal temperature, preserving the heat at 80 ℃ for 15min, and dropwise adding 3mol/L NaOH solution into the reaction product until the reaction product is clear and transparent to obtain a crude product; the crude product was transferred to a rotary evaporator and rotary evaporated to 20mL at 70 ℃. And adding ethanol solution with the volume 5 times that of the crude product after rotary evaporation, after aggregation and precipitation, centrifuging at the rotating speed of 8000rpm for 30min to obtain a product, repeating the step for three times, and freeze-drying the finally obtained product in a freeze dryer to obtain the solid copper nanocluster.
Example 5:
embodiment 5 of the present invention provides a method for preparing a copper nanocluster, including the steps of:
reduced glutathione (3.125 g) was dissolved in 100mL of ultrapure water at ordinary temperature to give an aqueous glutathione solution, and 4mL of 0 was added dropwise to the aqueous glutathione solution under vigorous stirring.5mol/L of Cu (NO)3)2After the solution is added, stirring the mixed solution at normal temperature until the color of the mixed solution fades and a milky hydrogel is gradually formed; when the milky-white hydrogel is not generated any more, heating the milky-white hydrogel to 80 ℃ from the normal temperature, preserving the heat at 80 ℃ for 15min, and dropwise adding 3mol/L NaOH solution into the reaction product until the reaction product is clear and transparent to obtain a crude product; the crude product was transferred to a rotary evaporator and rotary evaporated to 20mL at 70 ℃. And adding ethanol solution with the volume 5 times that of the crude product after rotary evaporation, after aggregation and precipitation, centrifuging at the rotating speed of 8000rpm for 30min to obtain a product, repeating the step for three times, and freeze-drying the finally obtained product in a freeze dryer to obtain the solid copper nanocluster.
The same amount of the solid copper nanoclusters prepared in examples 1 to 5 were taken and dissolved in water to prepare an aqueous solution of the copper nanoclusters, and the fluorescence emission spectra of the copper nanoclusters in examples 1 to 5 were measured at an excitation wavelength of 365nm and a maximum emission wavelength of 590nm, and the results shown in fig. 1 were obtained. As can be seen from fig. 1, the fluorescence emission intensity of the copper nanoclusters in examples 1 to 4 is sequentially increased, while the fluorescence emission intensity of the copper nanoclusters in example 5 is decreased, and the fluorescence emission intensity of the copper nanoclusters prepared in example 4 is strongest, that is, when the content of reduced glutathione (GSH for short) is low, the fluorescence emission intensity of the copper nanoclusters is weak, and the intensity is increased with GSH/Cu2+The molar ratio is increased, the fluorescence intensity of the obtained copper nanoclusters is continuously enhanced, and the fluorescence intensity of the obtained copper nanoclusters is increased in GSH/Cu2+The maximum value is reached when the molar ratio is 4; with GSH/Cu2+The molar ratio continues to increase and the fluorescence intensity of the copper nanoclusters decreases, i.e. when GSH/Cu2+The resulting copper nanoclusters are optimal at a molar ratio of 4.
In order to more intuitively observe the morphological characteristics of the synthesized copper nanoclusters, the particle size distribution of the copper nanoclusters was obtained by a transmission electron microscope, and the copper nanoclusters synthesized in example 4 were observed as an example, and the results shown in fig. 2 were obtained. As can be seen from fig. 2, the particle size distribution of the synthesized copper nanoclusters is in the range of 1.5 ± 1nm, which conforms to the definition of the nanoclusters. In addition, the size distribution of the synthesized copper nanoclusters is relatively uniform, and the feasibility of preparing the copper nanoclusters by using the preparation method disclosed by the invention is proved. As can be seen from fig. 2, some particles are relatively large, which may be caused by aggregation due to the high energy of the synthesized copper nanoclusters under the bombardment of the high voltage electron beam. By careful measurement of high resolution transmission electron microscopy images of copper nanoclusters, we found lattice fringes where the interplanar spacing was about 0.206nm, which is attributable to the diffractive surface of face centered Cu (111). The above results demonstrate that the copper nanoclusters (GSH @ CuNCs) are successfully synthesized by the preparation method of the present invention.
Fig. 3 is an infrared spectrum of the copper nanoclusters synthesized in example 4. From figure 3 we can find that the ligand GSH exhibits a number of characteristic infrared absorption peaks: for example, at 1650-1750cm of C ═ O bonds in the carboxyl group-1The stretching vibration and the O-H bond of (2) are 1400cm-1And 920cm-1Two nearby strong bending vibration peaks; the N-H bond in the amino group is 3400cm-1Near peak of stretching vibration and at 1610cm-1The bending vibration peak of (1); furthermore, at 2508cm-1The relatively weak absorption peak observed can be attributed to stretching vibration of the S-H bond. The distribution of characteristic peaks of the synthesized copper nanoclusters was substantially identical to that of the ligand glutathione with respect to the infrared spectrum of the ligand, with only a slight shift in peak appearance position. In addition, the stretching vibration peak of the S-H bond completely disappeared in the copper nanocluster, further indicating that the cleavage of the S-H bond and the binding of glutathione molecules to the surface of the copper nanocluster through the formation of the Cu-S bond.
Fig. 4 is an XPS spectrum of the copper nanoclusters synthesized in example 4. As can be seen from fig. 4, the synthesized copper nanoclusters have two distinct characteristic peaks 951.88eV and 931.98eV, which correspond to Cu 2p, respectively1/2And 2p3/2Can be attributed to Cu (0). And the absence of a characteristic peak at 942eV means that no Cu is present in the synthesized copper nanocluster2+. Furthermore, it is very important: 2p due to Cu (0)3/2The binding energy is very similar to that of Cu (I), differing only by 0.1 eV. Therefore, the valence states of copper in the obtained copper nanocluster may be located at 0 and +1 valence statesIn the meantime.
The results in fig. 2 to 4 all confirm the feasibility of synthesizing the copper nanoclusters by the method of the present invention, and the copper nanoclusters can be successfully prepared by the synthesis method of the present invention.
Test example 1:
the solid copper nanoclusters prepared in example 4 were taken and prepared into solutions with different concentrations, and the SOD inhibition effect thereof was detected by using a SOD (short for superoxide dismutase) kit (purchased from tokyo institute of biotechnology engineering), the SOD inhibition effect of the copper nanocluster solutions with copper nanocluster concentrations of 60mg/L, 120mg/L and 180mg/L was detected, respectively, and the solution containing no copper nanocluster was used as a blank control group, the detection wavelength was 450nm and the readings of a microplate reader were read, to obtain the results shown in fig. 5. From the results of fig. 5, it can be seen that the superoxide anion radical interacts with the copper nanoclusters, and as the concentration of the copper nanoclusters increases, the ultraviolet spectrum of the copper nanoclusters has a significantly reduced trend at 450nm, indicating that the higher the concentration of the copper nanoclusters is, the better the SOD inhibition effect is.
Test example 2:
taking the solid copper nanoclusters prepared in the embodiment 4, preparing copper nanocluster solutions with copper nanocluster concentrations of 60mg/L, 120mg/L and 180mg/L respectively, taking 4 same cigarettes, adding 0.2mL of the copper nanocluster aqueous solutions with different concentrations into a cigarette filter at normal temperature, standing for 30min, lighting the cigarettes, blowing air into the cigarette filter through an air pump, enabling smoke to pass through the cigarette filter, controlling the flow rate of the smoke in the cigarette filter to be 100mL per minute, introducing the smoke generated in half a minute into an INT solution containing an indicator, wherein the INT concentration is 1.5mmol/L and the INT solution amount is 15mL, slightly shaking the INT solution after the smoke is introduced, and detecting the ultraviolet spectrum absorption intensity of the INT solution at 505nm to obtain the result shown in fig. 6. As can be seen from FIG. 6, the simple INT hardly has ultraviolet absorption at 505nm, but the absorption intensity of the cigarette smoke is obviously increased at about 505nm after the cigarette smoke is introduced into the iodonitrotetrazole violet solution, and the result shows that the superoxide anion free radicals contained in the cigarette smoke interact with the copper nanoclusters, and in addition, as the concentration of the copper nanoclusters in the filter tip is increased, the ultraviolet spectrum of the cigarette smoke has an obvious reduction trend at 505nm, and the higher the concentration of the copper nanoclusters is, the better the scavenging effect of the superoxide anion free radicals in the smoke is.
Test example 3:
the solid copper nanoclusters prepared in example 4 were subjected to cytotoxicity test by the following method:
the cytotoxicity of the copper nanoclusters (GSH-CuNCs) of the present invention was measured by CCK8 standard colorimetry using PC12 cells as a subject of study. 100 μ L of the cell suspension was added dropwise to a 96-well plate, wherein the cell density was 10000 cells per well; cells were placed in 5% CO which had reached 37 ℃2Carrying out adherent growth in a cell culture box with saturated humidity for 24 hours, taking out liquid in a well-grown pore plate, and adding GSH-CuNCs (with the concentration of 1, 10, 20, 60 and 120 mg.L in sequence) with different concentrations into the pore plate-1) And a blank control group without GSH-CuNCs, and further incubation in an incubator for 24 hours, and finally 10. mu.L of CCK8 solution was added to the wells and then incubation was continued for 4 hours, and absorbance at 450nm was measured by a microplate reader. The operating table and tools used in the experiment need to be sterilized in advance, and the experiment operating process needs to be operated near the flame of the alcohol lamp. The results shown in FIG. 7 were obtained.
As can be seen from FIG. 7, the survival rate of PC12 cells gradually decreased with increasing concentration of GSH-CuNCs. GSH-CuNCs (1, 10 mg. L) at lower concentrations-1) The cell viability was slightly higher than that of the blank, but the cell viability was slightly lower than that of the blank but did not significantly affect the cell viability as the concentration of copper nanoclusters was increased, even when GSH-CuNCs was used at a concentration of 120 mg.L-1The cell survival rate is still above 85%. From the above results, it can be seen that the copper nanoclusters prepared in the present invention have little toxic and side effects on cells, and can be used in cigarette filters.
The above-described embodiments of the present invention should not be construed as limiting the scope of the present invention. Any other corresponding changes and modifications made according to the technical idea of the present invention should be included in the protection scope of the claims of the present invention.

Claims (6)

1. Use of copper nanoclusters for scavenging superoxide anion radicals in cigarettes, said copper nanoclusters being prepared by the steps of: mixing a copper source aqueous solution and a glutathione aqueous solution, and stirring at normal temperature to obtain milky hydrogel; heating the milky hydrogel to 75-85 ℃, and preserving heat for 10-20 min to obtain a reaction product; dropwise adding NaOH solution into the reaction product until the reaction product is clear and transparent to obtain a crude product; cooling the crude product to normal temperature, and purifying and separating to obtain copper nanoclusters; wherein the molar ratio of the copper source to the glutathione is 1: 1-5;
the crude product is purified and separated by ethanol solution, and the following method is adopted specifically: adding an ethanol solution into the crude product, aggregating and precipitating, and then centrifugally separating the mixed solution; the volume ratio of the ethanol solution to the crude product is 4-5: 1, the concentration of the ethanol solution is 95%;
the application comprises the steps of preparing a copper nanocluster aqueous solution, soaking a cigarette filter tip into the copper nanocluster aqueous solution at normal temperature for 20-40 min, igniting the cigarette and blowing air into the cigarette filter tip to enable smoke to pass through the cigarette filter tip, and detecting superoxide anion free radicals in the smoke through ultraviolet spectrum by taking iodonitrotetrazole violet as an indicator.
2. The use according to claim 1, wherein the copper source is any one of copper sulfate, copper nitrate, copper chloride; the glutathione is reduced glutathione.
3. The use according to claim 1, wherein the molar ratio of the copper source to glutathione is 1: 4.
4. the use according to claim 1, wherein the concentration of the aqueous copper nanocluster solution is 60 to 180 mg/L.
5. The use of claim 1, wherein the air is blown into the cigarette filter to keep the flow rate of the gas in the cigarette filter at 80-120 mL/min.
6. The use according to claim 1, wherein the ultraviolet spectrum detection is carried out by detecting the ultraviolet spectrum absorption intensity of the iodonitrotetrazole violet at 505nm after the smoke is introduced so as to judge the scavenging degree of superoxide anion free radicals in the cigarette; if the removal degree is higher, the ultraviolet absorption value of the iodine nitrotetrazole violet at 505nm after the smoke is introduced is lower; if the removal degree is lower, the ultraviolet absorption value of the iodonitrotetrazole violet at 505nm after the smoke is introduced is higher.
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