CN114561213B - Method for synthesizing functionalized selenium-doped carbon quantum dots and elemental selenium in one step and application - Google Patents
Method for synthesizing functionalized selenium-doped carbon quantum dots and elemental selenium in one step and application Download PDFInfo
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- CN114561213B CN114561213B CN202210198085.3A CN202210198085A CN114561213B CN 114561213 B CN114561213 B CN 114561213B CN 202210198085 A CN202210198085 A CN 202210198085A CN 114561213 B CN114561213 B CN 114561213B
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Abstract
The invention belongs to the technical field of materials, and discloses a method for synthesizing functionalized selenium-doped carbon quantum dots and elemental selenium in one step and application thereof. The method comprises the following steps: (1) Reducing a selenium precursor to form elemental selenium by using a carbon-containing substance as a carbon source and a reducing agent, and synthesizing selenium-doped carbon quantum dots by heating, carbonizing and cracking the carbon source; and (2) synthesizing and separating the elemental selenium. The invention takes carbon-containing substances as a carbon source and a reducing agent to reduce a selenium precursor to generate elemental selenium, and synthesizes the functionalized selenium-doped carbon quantum dots and the elemental selenium by one step through a microwave method or a hydrothermal method. The method has the characteristics of short time consumption, simple operation, greenness and high efficiency; the synthesized carbon quantum dots endow selenium with functional characteristics, the elemental selenium has different crystal structures, and the carbon quantum dots and the elemental selenium have wide application prospects in the fields of solar cells, photodetectors, display illumination, biology, detection and catalysis, and further widen the application fields of the quantum dots and the elemental selenium.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a method for synthesizing functionalized selenium-doped carbon quantum dots and elemental selenium in one step and application thereof.
Background
The quantum dots refer to a low-dimensional semiconductor material with the particle size of 0.2-10 nm and the influence of quantum confinement effect on three dimensions. The material has the advantages of small size, strong photoluminescence property, high stability, chemical inertness and environmental friendliness, and can be widely applied to the fields of photodetectors, solar cells and display illumination; in addition, compared with metal quantum dots, the low toxicity and high biocompatibility of the carbon quantum dots enable the carbon quantum dots to have wide application prospects in the biological field, such as living cell fluorescent labeling, tumor diagnosis, biological imaging, ion or pathogen detection and the like. At present, the synthesis methods of carbon quantum dots mainly comprise two types, namely top-down and bottom-up, wherein the top-down method refers to a method for peeling carbon nano particles on a large-size carbon source by a physical or chemical method and comprises an electrochemical method, a laser ablation method and a chemical oxidation method; the carbon quantum dots are directly prepared from a carbon-containing precursor as a material through polymerization and carbonization processes from bottom to top, and the method comprises a hydrothermal method, a microwave method and the like. Compared with the top-down method, the method has the advantages of simple operation, low cost and high yield, and is put into use on a large scale.
The directly synthesized carbon quantum dots have the problems of low quantum yield, poor fluorescence stability and the like, and the application of the carbon quantum dots is limited. The fluorescence performance can be improved by technical methods such as surface modification and element doping. Selenium (Se) is one of essential trace elements for human body and has close relationship with human health. Elemental selenium is one of the forms of selenium in nature, and has six allotropes, including amorphous selenium in amorphous state, glass state, and the like, and crystalline selenium in alpha-monoclinic state, beta-monoclinic state, gamma-monoclinic state, gray black trigonal system selenium, and the like. Researches find that the amorphous elemental selenium has the same or higher biological activity of oxidation resistance, cancer resistance and the like as inorganic selenium and organic selenium, has low toxicity, gradually becomes a novel selenium supplement and is widely applied in the biological field. Meanwhile, the amorphous selenium and the crystalline selenium both have narrow forbidden band widths and good photoelectric characteristics, and are widely applied to the fields of optics, electrics, magnetics and the like. Selenium as a doping element can not only improve the fluorescence property of the selenium, but also endow the selenium with biological activity.
The invention synthesizes the functionalized selenium-doped carbon quantum dots and elemental selenium in one step, and successfully overcomes the defects of single product and the like in the process of synthesizing the quantum dots in the prior art. Provides a new method and a new idea for the synthesis of selenium-doped carbon quantum dots and elemental selenium.
Disclosure of Invention
In order to overcome the defects of single product and the like in the process of synthesizing quantum dots in the prior art, the invention mainly aims to provide a method for synthesizing functionalized selenium-doped carbon quantum dots and elemental selenium in one step; under the condition of adding or not adding a stabilizing agent, reducing the selenium precursor by taking excessive different carbon-containing substances as a precursor and a reducing agent to form elemental selenium, synthesizing carbon quantum dots by heating and cracking and carbonizing the carbon-containing precursor, and simultaneously combining the generated selenium atoms with the carbon quantum dots to synthesize selenium-doped carbon quantum dots, endow the carbon quantum dots with functional activity, and synthesize the functionalized selenium-doped carbon quantum dots and the elemental selenium in one step; in addition, selenium-doped carbon quantum dots with obvious differences in selenium content and fluorescence performance and elemental selenium with different crystal structures can be obtained by changing heating conditions.
The invention also aims to provide the selenium-doped carbon quantum dot and the elemental selenium prepared by the preparation method.
The invention further aims to provide application of the selenium-doped carbon quantum dots and the elemental selenium, and the obtained selenium-doped carbon quantum dots and elemental selenium can be applied to the fields of optics, electrics, magnetism, biology and the like.
The purpose of the invention is realized by the following technical scheme:
a method for synthesizing functionalized selenium-doped carbon quantum dots and elemental selenium in one step comprises the following steps:
(1) Synthesizing the selenium-doped carbon quantum dots: under the microwave heating condition or the direct heating and pressurizing condition, with or without adding a stabilizer, the selenium precursor solution and the excessive carbon-containing substance solution are subjected to reduction reaction to generate elemental selenium, meanwhile, the redundant carbon-containing substance solution is subjected to heating cracking and carbonization to synthesize carbon quantum dots, and the carbon quantum dots are combined with part of elemental selenium to form selenium-doped carbon quantum dots; cooling to room temperature, adding an equal volume of solvent for resuspension, centrifuging to obtain supernatant and precipitate, filtering the supernatant, and directly obtaining or obtaining selenium-doped carbon quantum dot solution after dialysis;
the molar ratio of the selenium precursor in the selenium precursor solution to the carbon-containing substance in the carbon-containing substance solution is 1:2-1;
the power of the microwave is 80-800W, and the microwave heating time is 2-30 min;
the direct heating and pressurizing adopt water bath heating, oil bath heating or high-pressure reaction kettle heating, the specific heating temperature is 60-350 ℃, the heating time is 0-24 h, and the pressurizing pressure is 0-10MPa;
(2) Synthesizing and separating elemental selenium: and (2) adding a solvent into the precipitate obtained in the step (1) for resuspension to obtain an elemental selenium resuspension liquid, or freeze-drying the precipitate to obtain an elemental selenium solid.
The microwave heating in the step (1) is carried out in a microwave oven or a light wave oven; the direct heating and pressurizing are carried out in a constant-temperature water bath kettle, a constant-temperature oil bath kettle or a high-pressure reaction kettle.
The stabilizing agent in the step (1) is a surfactant containing hydroxyl, amino, carboxyl, carbonyl groups and hydrophobic regions, a high molecular polymer, a biological extract or a mixture of the above substances in any proportion; the addition amount of the stabilizer is 25-3000 mg/L.
The biological extract is animal extract, plant extract or microorganism extract, and specifically comprises flavonoids, tannins, phenols, saccharides, biomacromolecule protein, biomacromolecule polysaccharide, biomacromolecule protein and biomacromolecule polysaccharide complex, and biopolymer.
The selenium precursor in the step (1) is selenium dioxide, selenious acid, sodium selenite, selenate or sodium selenate; the concentration of the selenium precursor solution is 1-100 mM.
The carbon-containing substance in the step (1) is ascorbic acid, sodium ascorbate, citric acid, sodium citrate, reducing sugar, thiourea and polyphenol substances, or a mixture of the substances in any proportion; when the carbonaceous matter is a single substance, the solution concentration is 4-500 mM, and when the carbonaceous matter is a mixture, the solution concentration is 10-100 g/L.
The room temperature in the step (1) is 20-30 ℃; the centrifugation is carried out for 2-40 min at the rotating speed of 0-11000 r/min at the temperature of 4-25 ℃; the filtration is to filter the supernatant through a 0.22 μm filter membrane; the dialysis is carried out for 12 to 72 hours by adopting a 500 to 1000Da dialysis bag.
Preferably, the stabilizer in step (1) is water extract of camellia plant; the adding amount of the camellia plant water extract is 500mg/L; the selenium precursor is sodium selenite, the carbon-containing substance is vitamin C, and the molar ratio of the selenium precursor in the selenium precursor solution to the carbon-containing substance in the carbon-containing substance solution is 1:8; the power of the microwave is 800W, and the microwave treatment time is 8min; the direct heating and pressurizing are carried out by adopting water bath heating, the heating temperature is 100 ℃, and the heating time is 10 hours.
The solvent in the steps (1) and (2) is polar or nonpolar solvent, and comprises ultrapure water, ethanol, methanol, dichloromethane and trichloromethane.
Centrifuging the sediment obtained by the centrifugation in the step (2) at the rotating speed of 2000-11000 r/min for 2-40 min at the temperature of 4-25 ℃, repeatedly centrifuging for 2-5 times, and removing redundant supernatant.
Selenium-doped carbon quantum dots and elemental selenium prepared according to the method.
The selenium-doped carbon quantum dots and the elemental selenium are applied to the fields of solar cells, photodetectors, display illumination, biology, detection and catalysis.
The basic characteristics of the selenium-doped carbon quantum dots and the elemental selenium obtained by the method are evaluated by representing the morphological appearance, the surface functional group composition and structure, the crystal structure and the like of the selenium-doped carbon quantum dots and the elemental selenium through an atomic force microscope, a Fourier infrared spectrum, an X-ray diffractometer, an X-ray photoelectron spectrum, a Raman spectrum and the like; the Zeta potentials of the selenium-doped carbon quantum dots and the elemental selenium are measured through a laser Doppler velocity measurement technology, and the electrostatic stability of the selenium-doped carbon quantum dots and the elemental selenium obtained by the method is evaluated; and measuring the characteristic absorption peak, energy band gap and fluorescence intensity of the substance composition through ultraviolet-visible absorption spectrum and fluorescence spectrum respectively, and evaluating the optical characteristics of the selenium-doped carbon quantum dot.
Detecting the survival rate of tumor cells by an MTT method, and evaluating the anticancer activity of the selenium-doped carbon quantum dots; evaluating the anti-inflammatory activity of the selenium-doped carbon quantum dots by an anti-inflammatory method and an inflammatory cell model; evaluating the antioxidant activity of the selenium-doped carbon quantum dots and the elemental selenium obtained by the method through a chemical antioxidant method and an antioxidant cell model; evaluating the application of the selenium-doped carbon quantum dots in the biological field by carrying out fluorescence labeling and ion detection on living cells; the application of the selenium-doped carbon quantum dots and the elemental selenium in the fields of adsorption, photodegradation and photocatalysis is evaluated by adsorbing and degrading pollutants or toxic and harmful substances.
The tumor cell model comprises: human colorectal adenocarcinoma HCT 116 cell line, mouse liver cancer Hepa1c1c7 cell line, human breast cancer MDA-MB-231 cell line, human epithelial breast cancer BT-474 cell line, human embryonic kidney 239T and 293A3 cell line, human liver cancer HepG2 cell line, human liver cancer SMMC-7721 cell line, thyroid cancer SW579 cell line, human cervical cancer Hela cell line and other human and mouse in-vitro tumor cell models, preferably human colorectal adenocarcinoma HCT 116 cell line.
The chemical anti-inflammatory method is referred to Tsai et al.
The inflammatory cell model comprises: mouse monocyte macrophage leucocythemia cell Raw 264.7 cell line, human colorectal adenocarcinoma cell Caco-2 cell line, human umbilical vein vascular endothelial HUVEC cell line, human colon adenocarcinoma HT-29 cell line and other human and mouse in-vitro inflammatory cell models, preferably mouse monocyte macrophage leucocythemia cell Raw 264.7 cell line.
The above anti-inflammatory activity assay: chemical anti-inflammatory and cellular methods, preferably cellular methods.
The above antioxidant method is referred to Sharma et al.
The antioxidant cell model comprises: human liver cancer HepG2 cell line, human neuroblastoma SH-SY5Y cell line, mouse embryo fibroblast MEF cell line, NIH3T3 cell line, mouse monocyte macrophage leukemia cell Raw 264.7 cell line and other human and mouse in-vitro antioxidant cell models, preferably human liver cancer HepG2 cell line.
The antioxidant activity is measured as follows: chemical antioxidation and cell method, preferably cell method.
Fluorescence labeling of the living cells: mouse mononuclear macrophage leukemia cell Raw 264.7 cell line, human colorectal adenocarcinoma HCT 116 cell line, human breast cancer MDA-MB-231 cell line, human liver cancer HepG2 cell line, etc., preferably human liver cancer HepG2 cell.
The ion detection aspect is applied as follows: selenium doped carbon quantum dot selectivity to Fe 3+ In response, fe only 3+ Can quench the fluorescence of the carbon quantum dots, and the carbon quantum dots provided by the invention can be used for quenching the fluorescence of the carbon quantum dots 3+ The detection limit reaches 0.024 mu mol/L.
The above-mentioned adsorption, photodegradation, photocatalytic pollutants or toxic harmful substances include: organic dyes such as congo red, methylene blue, rhodamine B and the like; pyrethroid pesticides such as efficient cyhalothrin, imidacloprid, acetamiprid and the like and organophosphorus pesticides such as paraoxon, methyl parathion, parathion and the like.
Compared with the prior art, the invention has the following advantages and beneficial effects:
on the basis of preparing nano selenium by a soft template method, reducing a selenium precursor to generate elemental selenium by using carbon-containing substances as a carbon source and a reducing agent, and synthesizing functionalized selenium-doped carbon quantum dots and elemental selenium in one step by heating and cracking; the method has the characteristics of short time consumption, simple operation, greenness and high efficiency; the synthesized carbon quantum dots have excellent fluorescence performance and high luminescence stability, and have the functional characteristic of nano selenium; in addition, the method can obtain the elemental selenium with different crystal structures, and the elemental selenium have wide application prospects in the fields of solar cells, photodetectors, display illumination, biology and detection and catalysis, further broaden the application fields of quantum dots and elemental selenium and improve the application value of the elemental selenium.
Drawings
FIG. 1 shows UV-vis spectra (A) and fluorescence spectra (B) of selenium-doped carbon quantum dots synthesized at different microwave powers and obtained directly without dialysis.
FIG. 2 shows UV-vis spectra (A) and fluorescence spectra (B) of Se-doped carbon quantum dots synthesized at different microwave powers and obtained after dialysis.
Fig. 3 shows UV-vis spectra (a) and fluorescence spectra (B) of selenium-doped carbon quantum dots synthesized at different microwave times and directly obtained without dialysis.
FIG. 4 shows UV-vis spectra (A) and fluorescence spectra (B) of Se-doped carbon quantum dots synthesized at different microwave times and obtained after dialysis.
Fig. 5 is a UV-vis spectrum (a) and a fluorescence spectrum (B) of selenium-doped carbon quantum dots synthesized at different water bath heating temperatures and directly obtained without dialysis.
Fig. 6 shows UV-vis spectra (a) and fluorescence spectra (B) of selenium-doped carbon quantum dots synthesized at different water bath heating times and directly obtained without dialysis.
Fig. 7 shows XRD results of selenium-doped carbon quantum dots (a) and elemental selenium (B and C) obtained under different centrifugation conditions.
Fig. 8 shows XRD results of selenium-doped carbon quantum dots (a) and elemental selenium (B) obtained by heating in a water bath.
FIG. 9 shows UV-vis spectrum (A), fluorescence spectrum (B) and Zeta potential (C) of selenium-doped carbon quantum dots synthesized without or with different types of stabilizers.
Fig. 10 shows UV-vis spectra (a), fluorescence spectra (B) and Zeta potential (C) of selenium-doped carbon quantum dots synthesized with different selenium precursor species.
FIG. 11 shows UV-vis spectra (A), fluorescence spectra (B) and Zeta potential (C) of selenium-doped carbon quantum dots synthesized from different carbon-containing substances.
FIG. 12 shows the UV-vis spectrum (A), the fluorescence spectrum (B) and the Zeta potential (C) of the selenium-doped carbon quantum dot synthesized by a mixture of carbon-containing substances compounded in a certain proportion.
FIG. 13 is an atomic force microscope 2D image (A) of selenium-doped carbon quantum dots synthesized by microwave method; a selenium-doped carbon quantum dot atomic force microscope 3D picture (B); the height analysis (C) was performed for (1) and (2) in the graph (A).
Fig. 14 is a TEM image of a hydrothermally synthesized selenium-doped carbon quantum dot.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto. The equipment and the reagent used in the invention are all commonly used in the field. It should be understood that the examples described herein are for illustrative purposes only and are not intended to limit the present invention.
Example 1: a method for synthesizing functionalized selenium-doped carbon quantum dots and elemental selenium by microwave-assisted heating.
Dissolving a certain amount of Pu her tea water extract (500 mg/L) in ultrapure water, adding 8mL Vc solution (500 mM), magnetically stirring for 5min, standing for 15min, adding 5mL Na 2 SeO 3 Magnetically stirring the solution (100 mM), reacting for 5min, microwave heating at 0, 160, 320, 480, 640, 800W for 6min, cooling to room temperature, adding ultrapure water of equal volume for redissolving, centrifuging at 4 deg.C and 6000r/min for 10min to obtain supernatant and precipitate, and passing the supernatant through 0A 22 μm filter membrane directly obtained without dialysis or dialyzed by an 800Da dialysis bag for 24h to obtain selenium-doped carbon quantum dots, and the UV-vis spectrum and fluorescence spectrum of the selenium-doped carbon quantum dots are measured, as shown in figures 1 and 2, when the microwave power is 0, no fluorescence emission peak exists; and (4) freezing and drying the precipitate to obtain elemental selenium.
Example 2: a method for synthesizing functionalized selenium-doped carbon quantum dots and elemental selenium by microwave-assisted heating.
Compared with example 1, the difference is only that:
controlling the microwave power to be 800W, changing the microwave time to be 0, 2, 4, 6, 8 and 10min, synthesizing the selenium-doped carbon quantum dots and the elemental selenium, and measuring the UV-vis spectrum and the fluorescence spectrum of the selenium-doped carbon quantum dots, wherein the result is shown in fig. 3 and 4, and when the microwave time is 0min, no fluorescence emission peak exists.
Example 3: a method for synthesizing functionalized selenium-doped carbon quantum dots and elemental selenium by microwave-assisted heating.
Compared with example 1, the difference is only that:
controlling the microwave power to be 800W and the microwave time to be 8min, selecting a cellulose dialysis bag with MW of 100-500 Da for dialysis for 48h to remove impurities, and synthesizing the selenium-doped carbon quantum dots and the elemental selenium.
Example 4: a method for synthesizing functionalized selenium-doped carbon quantum dots and elemental selenium by a hydrothermal method.
Dissolving a certain amount of Pu her tea water extract (500 mg/L) in ultrapure water, adding 8mL Vc solution (500 mM), magnetically stirring for 5min, standing for 15min, adding 5mL Na 2 SeO 3 The solution (100 mM) is stirred magnetically for 5min, the solution is placed in a water bath at 60 ℃, 80 ℃ and 100 ℃ for heating for 10h, the solution is placed in an ice-water mixture and cooled to room temperature, the solution is centrifuged at 4 ℃ and 6000r/min for 10min to obtain supernatant and precipitate, the supernatant passes through a 0.22 mu m water system filter membrane, the selenium-doped carbon quantum dots are directly obtained without dialysis, and the UV-vis spectrum and the fluorescence spectrum of the selenium-doped carbon quantum dots are measured, as shown in figure 5, when the solution is heated in the water bath for 10h and the temperature is higher than 60 ℃, the fluorescence intensity is obviously increased, the fluorescence intensity is maximum when the water bath temperature is 100 ℃, the heating temperature is 60-100 ℃, and the maximum excitation wavelength of ultraviolet absorption is unchanged. And (4) freezing and drying the precipitate to obtain elemental selenium.
Example 5: a method for synthesizing functionalized selenium-doped carbon quantum dots and elemental selenium by a hydrothermal method.
Compared with example 4, the difference is only that:
the water bath temperature was controlled at 100 ℃, the water bath heating time was changed to 2, 4, 6, 8, 10, 12h, and the selenium-doped carbon quantum dots and elemental selenium were synthesized, and as a result, as shown in fig. 6, the fluorescence intensity of the selenium-doped carbon quantum dots increased with the increase of the water bath heating time, and the fluorescence intensity was the maximum when the heating time was 10h. The heating time is 2-12 h, and the maximum excitation wavelength of the ultraviolet absorption of the sample is unchanged.
Example 6: a method for synthesizing functionalized selenium-doped carbon quantum dots and elemental selenium by a hydrothermal method.
Compared with the embodiment 4, the difference points are that:
controlling the water bath temperature at 100 ℃, the water bath heating time at 10h, and dialyzing by using a cellulose dialysis bag with MW of 100-500 Da for 48h to remove impurities to synthesize selenium-doped carbon quantum dots and elemental selenium.
Example 7: a method for synthesizing functionalized selenium-doped carbon quantum dots and elemental selenium in one step.
Compared with example 1, the difference is only that:
controlling the microwave power to be 800W, synthesizing selenium-doped carbon quantum dots and elemental selenium for 8min by microwave, centrifuging at 4 ℃ and 2000r/min for 10min, respectively collecting supernatant and precipitate, adding equal amount of ultrapure water into the precipitate, changing the centrifugal rotating speed to be 4000, 6000, 8000 and 10000r/min, repeating the steps to obtain products in different centrifugal rotating speed ranges, and measuring the crystal structure of the products by an X-ray diffractometer. The result is shown in fig. 7, the selenium-doped carbon quantum dot is an amorphous carbon structure, and the elemental selenium is trigonal t-Se.
The difference from example 4 is only that:
controlling the water bath temperature at 100 ℃, synthesizing selenium-doped carbon quantum dots and elemental selenium for 10h in water bath heating time, centrifuging at 4 ℃ and 6000r/min for 10min, respectively collecting supernatant and precipitate, and measuring the crystal structure of the product by an X-ray diffractometer. The result is shown in fig. 8, the selenium-doped carbon quantum dot is an amorphous carbon structure, and the elemental selenium is trigonal t-Se.
Example 8: a method for synthesizing functionalized selenium-doped carbon quantum dots and elemental selenium by microwave heating.
Compared with example 1, the difference is only that:
controlling Vc in the reaction system: na (Na) 2 SeO 3 In a molar ratio of 8:1, no stabilizer is added or the Pu' er tea water extract, chitosan, PEG 6000, catechin extract, bovine serum albumin, glucose and the like are taken as the stabilizer. In the synthesis process, after the carbon-containing substance and the selenium precursor substance are mixed, the reaction time is 15min under magnetic stirring, after microwave-assisted heating, equal volume of ultrapure water is added for resuspension, and the UV-vis spectrum, the fluorescence spectrum and the Zeta potential of the selenium-doped carbon quantum dot are filtered through a 0.22 mu m filter membrane, and the result is shown in FIG. 9.
Example 9: a method for synthesizing functionalized selenium-doped carbon quantum dots and elemental selenium by microwave heating.
Compared with the embodiment 1, the difference points are that:
sodium selenite and selenium dioxide are respectively used as selenium precursor substances to synthesize selenium-doped carbon quantum dots and elemental selenium, and the UV-vis spectrum, the fluorescence spectrum and the Zeta potential of the selenium-doped carbon quantum dots are measured, and the result is shown in figure 10.
Example 10: a method for synthesizing functionalized selenium-doped carbon quantum dots and elemental selenium by microwave heating.
Compared with example 1, the difference is only that:
sodium ascorbate and glucose are taken as carbon-containing substances respectively, selenium-doped carbon quantum dots and elemental selenium are synthesized, and the UV-vis spectrum, the fluorescence spectrum and the Zeta potential of the selenium-doped carbon quantum dots are measured, and the result is shown in FIG. 11.
Example 11: a method for synthesizing functionalized selenium-doped carbon quantum dots and elemental selenium by microwave heating.
Compared with example 1, the difference is only that:
the method comprises the steps of synthesizing selenium-doped carbon quantum dots and elemental selenium by taking a mixture of ascorbic acid and glucose and a mixture of ascorbic acid and citric acid which are compounded in a certain proportion as carbonaceous substances, and measuring the UV-vis spectrum, the fluorescence spectrum and the Zeta potential of the selenium-doped carbon quantum dots, wherein the results are shown in figure 12.
Example 12: characterization of basic and optical properties of selenium-doped carbon quantum dots
The atomic force microscope, the Fourier infrared spectrum, the X-ray diffractometer, the X-ray photoelectron spectrum, the Raman spectrum and the like are adopted to represent the morphological appearance, the surface functional group composition and structure, the crystal structure and the like of the selenium-doped carbon quantum dots and the elemental selenium synthesized in the embodiments 3 and 6, and the basic characteristics of the selenium-doped carbon quantum dots and the elemental selenium obtained by the method are researched. The results show that the selenium-doped carbon quantum dots synthesized by the two methods are both in a quasi-spherical structure, have good monodispersity, have the particle size of about 2-5 nm (as shown in figures 13 and 14), contain abundant functional groups such as-OH, -N-H, -C = O and-C-O-on the surface, and chemical bonds such as C = C/C-C, C-O, O-C = O, C-Se, and are in an amorphous carbon structure; elemental selenium is a trigonal t-Se structure.
The Zeta potential of the selenium-doped carbon quantum dots is measured by adopting a laser Doppler velocity measurement technology, and the electrostatic stability of the selenium-doped carbon quantum dots is researched. The results show that: the Zeta potential values of the selenium-doped carbon quantum dots are all about 30mV, and the selenium-doped carbon quantum dots are negatively charged and have high electrostatic stability.
Ultraviolet-visible absorption spectrum and fluorescence spectrum are adopted to measure the characteristic absorption peak, energy band gap and fluorescence intensity of the material composition, and the optical characteristics of the selenium-doped carbon quantum dots are researched. The results show that: the maximum characteristic absorption peak of the selenium-doped carbon quantum dot is 261nm, the maximum excitation wavelength is 280nm, the maximum emission wavelength is 452nm, and the energy level band gap is 3.79eV.
Example 13: determination of selenium-doped carbon quantum dot anticancer activity
The antiproliferative activity of the selenium-doped carbon quantum dots synthesized in example 3 on HCT 116 cells was determined using the MTT method. Adherent HCT 116 cells were trypsinized to make single cell suspensions at 5X 10 4 The individual cells/well were seeded in 96-well plates at 37 ℃ and 5% CO 2 Pre-culturing for 24h in an incubator, diluting selenium-doped carbon quantum dots with different concentrations with a culture medium (calculating the adding concentration according to the selenium content), and then carrying out 10-step cultureThe medium was added at 0. Mu.L/well and the culture was continued for 24 hours. Adding 0.05mg/mL MTT dilution 100. Mu.L/well to the plate, standing at 37 ℃ and 5% CO 2 Continuously culturing in the incubator for 2h, removing supernatant, adding 200 μ L DMSO solution into each well, placing in a shaking table at 100r/min, shaking for 15-20 min, and measuring OD of each well 550 Value as control OD 550 The value is 100%, and the half Inhibitory Concentration (IC) of the selenium-doped carbon quantum dots for inhibiting cell proliferation is calculated 50 ). The results show that: IC of selenium-doped carbon quantum dots for inhibiting HCT 116 cells 50 Comprises the following steps: 5.88. + -. 0.04. Mu. Mol/L (calculated as concentration of added Se).
Example 14: selenium-doped carbon quantum dot detection of Fe 3+
Diluting the selenium-doped carbon quantum dot solution synthesized in example 3 by 50 times, and adding FeCl with different concentrations in equal volume 3 The solutions (1.5625, 3.1250, 6.2500, 12.5000, 25.0000, 50.0000, 100.0000, 200.0000, 300.0000. Mu. Mol/L) were mixed well, left to stand for 0.5min, and their fluorescence emission spectra and fluorescence intensity values were measured at an excitation wavelength of 380nm to obtain Fe 3+ The correlation with the fluorescence intensity establishes Fe 3+ And (5) a detection method, namely calculating to obtain a detection Limit (LOD). The results show that: in Fe 3+ The concentration is 1.5625-200.0000 mu mol/L, fe 3+ Has a better linear relation with the fluorescence intensity, and a linear curve is obtained through fitting: y = -0.00394x +1.0135 2 =0.9898.LOD is 0.024 mu mol/L
Example 15: selenium-doped carbon quantum dots and elemental selenium for adsorbing and degrading methylene blue
Aspirate 20mL of 1X 10 -5 Adding 5mL of the selenium-doped carbon quantum dots and the elemental selenium synthesized in the example 3 into a 25mL beaker respectively according to mol/L of the methylene blue solution, magnetically stirring and balancing the tin foil paper for 30min under the condition of keeping out of the sun, standing the tin foil paper for 0, 20 and 40min respectively, centrifuging the tin foil paper at 4 ℃ and 10000r/min for 8min, absorbing the supernatant, measuring the absorbance value by an ultraviolet-visible spectrophotometer with the wavelength of 665nm, and calculating the adsorption rate of the selenium-doped carbon quantum dots and the elemental selenium on the methylene blue, wherein the results are shown in Table 1.
TABLE 1 adsorption ratio (%)% of selenium-doped carbon quantum dots and elemental selenium to methylene blue
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. A method for synthesizing functionalized selenium-doped carbon quantum dots and elemental selenium in one step is characterized by comprising the following steps:
(1) Synthesizing the selenium-doped carbon quantum dots: under the microwave condition or the direct heating and pressurizing condition, with or without adding a stabilizer, the selenium precursor solution and the excessive carbon-containing substance solution are subjected to reduction reaction to synthesize elemental selenium, meanwhile, the redundant carbon-containing substance solution is subjected to heating cracking and carbonization to synthesize carbon quantum dots, and the carbon quantum dots are combined with part of elemental selenium to form selenium-doped carbon quantum dots; cooling to room temperature, adding an equal volume of solvent for resuspension, centrifuging to obtain supernatant and precipitate, filtering the supernatant, and directly obtaining or obtaining selenium-doped carbon quantum dot solution after dialysis;
the molar ratio of the selenium precursor in the selenium precursor solution to the carbonaceous material in the carbonaceous material solution is 1 to 2-1;
the power of the microwave is 80-800W, and the processing time of the microwave is 2-30 min;
the direct heating and pressurizing adopt water bath heating, oil bath heating or high-pressure reaction kettle heating, the specific heating temperature is 100 ℃, the heating time is 10h, and the pressurizing pressure is 0-10MPa;
the stabilizer is Pu' er tea water extract, chitosan, PEG 6000, catechin extract, bovine serum albumin or glucose;
the selenium precursor is selenium dioxide, selenious acid, sodium selenite, selenate or sodium selenate;
the carbonaceous substance is ascorbic acid, sodium ascorbate or glucose;
(2) Synthesizing and separating elemental selenium: and (2) adding a solvent into the precipitate obtained in the step (1) for resuspension to obtain an elemental selenium resuspension liquid, or freeze-drying the precipitate to obtain an elemental selenium solid.
2. The method of claim 1, wherein the method comprises the steps of: the addition amount of the stabilizer in the step (1) is 25-3000 mg/L.
3. The method of claim 1, wherein the method comprises the steps of: the concentration of the selenium precursor solution in the step (1) is 1 to 100 mM;
when the carbonaceous substance is a single substance, the solution concentration is 4 to 500mM, and when the carbonaceous substance is a mixture, the solution concentration is 10 to 100g/L.
4. The method of claim 1, wherein the method comprises the steps of: the microwave heating in the step (1) is carried out in a microwave oven or a light wave oven; the direct heating and pressurizing are carried out in a constant-temperature water bath kettle, a constant-temperature oil bath kettle or a high-pressure reaction kettle; the room temperature is 20 to 30 ℃; the centrifugation is carried out for 2 to 40min at the rotation speed of 0 to 11000r/min at the temperature of 4 to 25 ℃; the filtration is to pass the supernatant through a 0.22 mu m filter membrane; the dialysis is carried out for 12 to 72 hours by adopting a 500 to 1000Da dialysis bag.
5. The method of claim 1, wherein the method comprises the steps of: the stabilizer in the step (1) is a Pu' er tea water extract; the adding amount of the Pu' er tea water extract is 500mg/L; the selenium precursor is sodium selenite, the carbon-containing substance is vitamin C, and the molar ratio of the selenium precursor in the selenium precursor solution to the carbon-containing substance in the carbon-containing substance solution is 1:8; the power of the microwave is 800W, and the microwave treatment time is 8min; the direct heating and pressurizing are carried out by adopting water bath heating, the heating temperature is 100 ℃, and the heating time is 10h.
6. The method of claim 1, wherein the method comprises the steps of: the solvent in the steps (1) and (2) is polar or nonpolar solvent, and comprises ultrapure water, ethanol, methanol, dichloromethane and trichloromethane.
7. The method of claim 1, wherein the method comprises the steps of: centrifuging the precipitate obtained by the centrifugation in the step (2) for 2 to 40min at the rotating speed of 2000 to 11000r/min at the temperature of 4 to 25 ℃, repeatedly centrifuging for 2~5, and removing redundant supernatant.
8. Selenium-doped carbon quantum dots and elemental selenium prepared according to the method of any one of claims 1 to 7.
9. The use of selenium-doped carbon quantum dots and elemental selenium according to claim 8 in the field of solar cells, photodetectors, display lighting, biology, ion detection and catalysis.
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