CN115386366A - High-fluorescence quantum yield sulfur quantum dot with simulated oxidase activity and preparation and application thereof - Google Patents
High-fluorescence quantum yield sulfur quantum dot with simulated oxidase activity and preparation and application thereof Download PDFInfo
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- CN115386366A CN115386366A CN202211099763.7A CN202211099763A CN115386366A CN 115386366 A CN115386366 A CN 115386366A CN 202211099763 A CN202211099763 A CN 202211099763A CN 115386366 A CN115386366 A CN 115386366A
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- C09K11/56—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing sulfur
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- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/02—Sulfur; Selenium; Tellurium; Compounds thereof
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Abstract
The invention discloses a sulfur quantum dot with high fluorescence quantum yield and simulated oxidase activity, and a preparation method and an application thereof, wherein the preparation method comprises the following steps: mixing sublimed sulfur, sodium hydroxide, polyethylene glycol 400 and water, addingHot reflux to obtain solution A; adding ferrate, mixing, and reacting at the same temperature to obtain solution B; taking the supernatant of the solution B, and recording the supernatant as solution C; take H 2 O 2 And mixing with the solution C, and etching by hydrogen peroxide to generate sulfur quantum dots with high fluorescence quantum yield and simulated oxidase activity, which are marked as SQDs. The invention solves the problems of therapeutic effect loss and pathogenic bacteria drug resistance formation caused by long-term use of antibiotics, and provides a new method for detecting folic acid, which is simple and quick and has high specificity. The SQDs of the invention have oxidase activity and show excellent inhibition capability on typical pathogenic multi-drug resistant escherichia coli and methicillin resistant staphylococcus aureus.
Description
Technical Field
The invention relates to a quantum dot, in particular to a sulfur quantum dot with high fluorescence quantum yield and simulated oxidase activity, and preparation and application thereof.
Background
Folic Acid (FA) is an important water-soluble vitamin B, has various functions in the human body, such as acquisition, transportation, enzyme treatment and the like of carbon units involved in amino acid and nucleic acid metabolism, and is an essential substance for cell growth and reproduction. But is usually provided by diet since it cannot be synthesized by the human body. Normal levels of FA in serum are between 7 and 42nM, and deficiency can lead to a number of diseases such as fetal neural tube defects, cardiovascular disease, megaloblastic anemia, and the like. Studies have reported that the development of cancer is associated with low levels of FA as well. Therefore, it is very important to develop an accurate analysis technique for detecting FA. Quantum Dots (QDs) are an attractive fluorescent probe due to their size-tunable emission characteristics, narrow emission spectra, and high photoluminescence quantum yield (PLQY), and have been explored for the detection of various biomolecules. However, the use of sulfur quantum dots to determine FA has not been reported.
The problem of gram-bacteria infection, one of the current global public health problems, is a serious threat to human health, and the number of deaths due to infection with drug-resistant bacteria reaches millions each year. Since the discovery of penicillin, antibiotics have been a powerful weapon for human treatment of pathogenic microbial infectious diseases, and can inhibit cell wall synthesis and damage cell membranes, inhibit synthesis of DNA and RNA, and the like, and further interfere with basic physiological processes of bacteria. However, the bacteria can generate drug resistance through gene mutation or transmit the drug resistance to other strains through plasmids, and the long-term overuse of antibiotics causes the appearance of drug-resistant strains, reduces the therapeutic effect of the traditional antibiotics, even loses the curative effect in many cases, and the formation of drug resistance of pathogenic bacteria is becoming serious day by day. Therefore, it is necessary to search for and develop a novel antibacterial agent having high antibacterial activity. Due to the inherent antibacterial activity of elemental sulfur and the broad-spectrum antibacterial activity, non-drug resistance and high efficiency of nanomaterials, sulfur quantum dots are drawing attention as a novel potential broad-spectrum antibiotic. Although sulfur quantum dots have wide application in the fields of biosensing, food analysis, detection, photoelectric devices and the like, the application of sulfur quantum dots in bacteriostasis is rarely reported at present.
Disclosure of Invention
The invention aims to provide a sulfur quantum dot with high fluorescence quantum yield and oxidase activity simulation function, and preparation and application thereof, solves the problems of therapeutic effect loss and pathogenic bacteria drug resistance formation caused by long-term use of antibiotics, and provides a new method for detecting folic acid, wherein the method is simple and rapid, and has high specificity on folic acid.
In order to achieve the above object, the present invention provides a method for preparing sulfur quantum dots with high fluorescence quantum yield and mimic oxidase activity, the method comprising:
(1) Mixing sublimed sulfur, sodium hydroxide, polyethylene glycol 400 and water, and heating and refluxing to obtain a solution A;
(2) Mixing the solution A prepared in the step (1) with ferrate, and reacting at the same temperature as the step (1) to prepare solution B;
(3) Taking the supernatant of the solution B prepared in the step (2), and recording the supernatant as solution C;
(4) Mixing the solution C obtained in the step (2) with H 2 O 2 And mixing at room temperature, and etching by hydrogen peroxide to generate sulfur quantum dots with high fluorescence quantum yield and simulated oxidase activity, which are marked as SQDs.
Preferably, said sublimed sulfur,The mass volume ratio of the sodium hydroxide, the polyethylene glycol 400 and the water is 0.7g:2g:1.5mL:25mL; said H 2 O 2 The concentration of (b) is 1.6-6.5 mM, the solution C and H 2 O 2 Are equal in volume.
More preferably, said H 2 O 2 Was 4mM.
Preferably, the mass ratio of sublimed sulfur to ferrate is 21.875:0.151.
preferably, the temperature of the heated reflux is 70 ℃.
The invention provides a sulfur quantum dot prepared by the preparation method. The sulfur quantum dot emits blue fluorescence under the excitation of 370nm, and the fluorescence emission peak is located at 450nm; the sulfur quantum dots are spherical, and the particle size is 20-80 nm.
The invention provides application of the sulfur quantum dot in preparation of an antibacterial agent for inhibiting drug-resistant escherichia coli and/or methicillin-resistant staphylococcus aureus.
The invention provides application of the sulfur quantum dot in non-diagnostic folic acid detection.
The invention provides a method for detecting folic acid by using the sulfur quantum dot in non-diagnosis, which comprises the following steps:
and adding the sulfur quantum dots into a sample to be detected, reacting at the pH of 2-11, and determining the fluorescence intensity of a reaction solution at the wavelength of 450 nm.
Preferably, the pH is 7 to 11, and the reaction time is 1 to 10 minutes.
The invention relates to a sulfur quantum dot with high fluorescence quantum yield and oxidase activity simulation function, and preparation and application thereof, which solve the problems of therapeutic effect loss and pathogenic bacteria drug resistance formation caused by long-term use of antibiotics, and provide a new method for detecting folic acid, and have the following advantages:
(1) The SQDs provided by the invention have fluorescence stability when the pH is 2-10 or the temperature is 20-60 ℃ or the concentration of NaCl is 0-1.0M.
(2) The SQDs provided by the invention have extremely high fluorescence quantum yield which reaches 35.24%.
(3) The SQDs provided by the invention can be used as a fluorescent probe for directly detecting folic acid, the method is simple and quick, the specificity is high, and the detection limit is as low as 9.16 mu M.
(4) The SQDs provided by the invention are reported for the first time, and the sulfur quantum dot material with oxidase activity has the optimum pH of 3 and the optimum temperature of 40 ℃.
(5) The SQDs provided by the invention have excellent inhibition capability on typical pathogenic multidrug-resistant escherichia coli and methicillin-resistant staphylococcus aureus, specifically, the material concentration is less than or equal to 0.1mg/mL, and the growth of drug-resistant bacteria can be effectively inhibited.
Drawings
FIG. 1 is a diagram showing the optimization of the content of potassium ferrate synthesized from SQDs prepared in examples 1 to 7 of the present invention.
FIG. 2 shows the synthesis H of SQDs prepared in examples 1, 8 to 13 of the present invention 2 O 2 And (5) optimizing the graph.
FIG. 3 is an HRTEM image of SQDs prepared in example 1 of the present invention.
FIG. 4 is a graph showing a distribution of particle sizes of SQDs prepared in example 1 of the present invention.
FIG. 5 is a graph showing optical properties of SQDs prepared in example 1 of the present invention.
FIG. 6 is a graph showing the excitation dependence of SQDs prepared in example 1 of the present invention.
FIG. 7 is an XPS survey of SQDs prepared in example 1 of the present invention.
FIG. 8 is an XPS fine spectrum of the S element of SQDs prepared in example 1 of the present invention.
FIG. 9 is a FTIR spectrum of SQDs prepared in example 1 of the present invention.
FIG. 10 is a graph showing pH stability of SQDs prepared in example 1 of the present invention.
FIG. 11 is a graph showing the temperature stability of SQDs prepared in example 1 of the present invention.
FIG. 12 is a graph showing salt stability of SQDs prepared in example 1 of the present invention.
FIG. 13 is a graph showing the pH optimization of the SQDs test FA prepared in example 1 of the present invention.
FIG. 14 is a graph showing the time optimization of detection of FA by SQDs prepared in example 1 of the present invention.
FIG. 15 shows fluorescence specificity of detection FA from SQDs prepared in example 1 of the present invention.
FIG. 16 is a fluorescence spectrum of detected FA from SQDs prepared in example 1 of the present invention.
FIG. 17 is a standard curve diagram of the detection of FA in SQDs prepared in example 1 of the present invention, in which the FA concentration is plotted on the abscissa and the fluorescence intensity F 0 and/F is the ordinate.
FIG. 18 is a graph showing the optimum conditions for the oxidation-simulated enzymatic activities of SQDs prepared in example 1 of the present invention, wherein A is the relative activity measured at different pH values; b is the relative activity measured at different temperatures.
FIG. 19 is a graph showing the survival rate of SQDs against two drug-resistant bacteria at different concentrations, wherein A is the survival percentage of methicillin-resistant Staphylococcus aureus; b is the survival percentage of the multidrug-resistant Escherichia coli.
FIG. 20 shows the OD of the bacterial suspension after treatment of different material groups 600 The value is obtained.
FIG. 21 is a drawing of a petri dish after treatment of different material groups, wherein A is multi-drug resistant Escherichia coli, and C is multi-drug resistant Escherichia coli + SQDs; b is multidrug-resistant Escherichia coli, and D is methicillin-resistant Staphylococcus aureus + SQDs.
FIG. 22 is a graph showing fluorescence comparison of SQDs prepared in example 1 of the present invention with quinine sulfate.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The tablets and media used in the following experimental examples of the invention are as follows:
the tablet a is 0.4mg,31 tablets/box, chinese medicine standard H20003143, and Changzhou pharmaceutical factory Limited company;
tablet b is 0.4mg,100 tablets/box, national drug standard H36020872, jiangxi pharmaceutical Limited liability company;
tablet c is 0.4mg,93 tablets/box, national drug standard H20044917, jiangsu Union Ring pharmaceutical Co., ltd;
tablet d is 0.5mg,100 tablets/box, national drug standard H62020684, gansu blue drug industry Co., ltd;
the type of the culture medium is LB nutrient agar, the specification is 250g, and the Qingdao Haibo biotechnology is limited.
Example 1
A method for preparing a high fluorescence quantum yield sulfur quantum dot with simulated oxidase activity, the method comprising:
(1) Firstly, 0.7g of sublimed sulfur, 2g of sodium hydroxide, 1.5mL of polyethylene glycol 400 and 25mL of distilled water are mixed and refluxed for 4 hours at 70 ℃ to obtain solution A;
(2) Mixing 25mg of potassium ferrate in the solution A prepared in the step (1), continuously keeping the original reaction condition for reacting for 1 hour to obtain solution B;
(3) And (3) centrifuging the solution B prepared in the step (2) at 3500rpm for 5min, and then leaving a supernatant, wherein the supernatant is recorded as a solution C (25 mL).
(4) Mixing the solution C obtained in the step (2) with 4mMH 2 O 2 Equal volumes of mixing (25 mL) further assisted the etching to give SQDs.
Example 2
A method of preparing high fluorescence quantum yield sulfur quantum dots with simulated oxidase activity, the method being substantially the same as in example 1 except that:
the mass of the potassium ferrate in the step (2) is 2.5mg.
Example 3
A method of preparing high fluorescence quantum yield sulfur quantum dots with simulated oxidase activity, the method being substantially the same as in example 1 except that:
the mass of the potassium ferrate in the step (2) is 5.0mg.
Example 4
A method of preparing high fluorescence quantum yield sulfur quantum dots with simulated oxidase activity, the method being substantially the same as in example 1 except that:
the mass of the potassium ferrate in the step (2) is 12.5mg.
Example 5
A method of preparing high fluorescence quantum yield sulfur quantum dots with mimic oxidase activity, the method being substantially the same as in example 1 except that:
the mass of the potassium ferrate in the step (2) is 37.5mg.
Example 6
A method of preparing high fluorescence quantum yield sulfur quantum dots with simulated oxidase activity, the method being substantially the same as in example 1 except that:
the mass of the potassium ferrate in the step (2) is 50.0mg.
Example 7
A method of preparing high fluorescence quantum yield sulfur quantum dots with simulated oxidase activity, the method being substantially the same as in example 1 except that:
the mass of the potassium ferrate in the step (2) is 62.5mg.
Example 8
A method of preparing high fluorescence quantum yield sulfur quantum dots with mimic oxidase activity, the method being substantially the same as in example 1 except that:
step (4) H 2 O 2 The concentration of (2) was 1.6mM.
Example 9
A method of preparing high fluorescence quantum yield sulfur quantum dots with mimic oxidase activity, the method being substantially the same as in example 1 except that:
step (4) H 2 O 2 Was 2.4mM.
Example 10
A method of preparing high fluorescence quantum yield sulfur quantum dots with simulated oxidase activity, the method being substantially the same as in example 1 except that:
step (4) H 2 O 2 Was 3.2mM.
Example 11
A method of preparing high fluorescence quantum yield sulfur quantum dots with simulated oxidase activity, the method being substantially the same as in example 1 except that:
step (4) wherein H 2 O 2 Was 4.9mM.
Example 12
A method of preparing high fluorescence quantum yield sulfur quantum dots with simulated oxidase activity, the method being substantially the same as in example 1 except that:
step (4) H 2 O 2 Is 5.7mM.
Example 13
A method of preparing high fluorescence quantum yield sulfur quantum dots with mimic oxidase activity, the method being substantially the same as in example 1 except that:
step (4) H 2 O 2 The concentration of (2) was 6.5mM.
As shown in FIG. 1, the optimization chart of the content of synthetic potassium ferrate in the SQDs prepared in the examples 1-7 of the present invention; as shown in FIG. 2, synthesis H of SQDs prepared in examples 1, 8 to 13 of the present invention 2 O 2 And (5) optimizing the graph. As can be seen from FIGS. 1 to 2, the optimum amount of potassium ferrate to be incorporated is 25mg, and H is added 2 O 2 The optimum concentration of (3) is 4mM.
Experimental example 1 the SQDs prepared in example 1 were subjected to HRTEM, XPS and FTIR characterization
TEM images of SQDs prepared in example 1 are shown in FIG. 3. As can be seen from FIG. 3, the prepared SQDs are spherical and well dispersed.
As shown in FIG. 4, the particle size distribution of SQDs prepared in example 1 was shown. The mean diameter is 55nm as can be seen in FIG. 4.
As shown in FIG. 5, the optical property patterns of the SQDs prepared in example 1 were shown. As seen in FIG. 5, SQDs have absorption peak at 220nm, and emit bright blue fluorescence at 450nm under UV irradiation at 370 nm.
As shown in FIG. 6, the excitation dependence of SQDs prepared in example 1 was plotted. As shown in FIG. 6, the peak positions of the emission wavelengths of SQDs are unchanged at different excitation wavelengths.
As shown in FIG. 7, XPS total spectra of SQDs prepared in example 1 were obtained. The XPS spectrum represented by FIG. 7 shows that SQD is composed mainly of C, O and S.
As shown in FIG. 8, the S element XPS fine spectrum of the SQDs prepared in example 1. As shown in FIG. 8, the key element S in SQDs shows peaks at 162.28eV and 164.58eV corresponding to atomic sulfur, which indicates the successful synthesis of SQDs.
As shown in FIG. 9, FTIR spectra of SQDs prepared in example 1 were obtained. From FIG. 9, where 1143cm -1 、833cm -1 And 623cm -1 The successful synthesis of SQDs is confirmed by the stretching vibrations of (1) originating from the C-O bond, the S-O bond and the S-S bond, respectively, and further confirms the XPS result.
Therefore, as can be seen from fig. 7 to 9, the Sulfur Quantum Dots (SQDs) prepared in example 1 are characterized by XPS and FTIR, and it can be seen that ferrate and hydrogen peroxide are used as strong oxidants to successfully etch the sulfur dots into the sulfur quantum dots by continuously assisting the precipitation.
Experimental example 2 stability test of SQDs prepared in example 1
Under the condition of room temperature, adding 0.9 mLbuffer solution with the pH value of 2, 3, 4, 5, 6, 7, 8, 9 or 10 and 0.1mLSQDs into a 2ml polyethylene plastic pipe, uniformly mixing, pouring into a quartz cuvette after 1min of constant temperature water bath at 25 ℃ to measure the fluorescence intensity to verify the influence of the pH value on the fluorescence intensity of the SQDs; similarly, under the condition of optimal pH, 0.9mL of the buffer solution with the optimal pH and 0.1mL of the phosphate buffer quantum dots (SQDs) are added into a 2mL polyethylene plastic tube, the reaction system is put into water baths (20, 30, 40, 50 and 60 ℃) at different temperatures to react for 1min, and the quartz cuvette is poured to measure the fluorescence intensity to verify the influence of the temperature on the fluorescence intensity of the SQDs; under the conditions of keeping the optimal temperature and the optimal pH, 0.8mL of the buffer solution with the optimal pH, 0.1mLSQDs and 0.1mL of NaCl solutions (0-1M) with different concentrations are added into a 2mL polyethylene plastic tube, and the mixture is reacted for 1min and poured into a quartz cuvette to measure the fluorescence intensity so as to verify the influence of the salt concentration on the fluorescence intensity of the SQDs.
As shown in FIG. 10, the pH stability of SQDs prepared in example 1 was plotted. As can be seen from fig. 10, the normalized fluorescence intensity of the SQD remains substantially stable when the pH value is varied from 2 to 10, which means that the SQD exhibits excellent optical stability even under extreme pH conditions.
As shown in FIG. 11, the temperature stability of SQDs prepared in example 1 is shown. As seen in FIG. 11, as the temperature increases (20 ℃ C. To 60 ℃ C.), the fluorescence intensity slightly decreases, but the overall stability remains, so the normalized fluorescence intensity of SQD is less affected by the temperature.
As shown in FIG. 12, the salt stability profiles of SQDs prepared in example 1. As can be seen from FIG. 12, the fluorescence intensity of SQDs remained substantially stable when the NaCl concentration was increased from 0 to 1.0M, indicating that SQDs had a good salt-resistant effect, demonstrating excellent fluorescence stability of SQDs.
Therefore, it can be understood from FIGS. 10 to 12 that the Sulfur Quantum Dots (SQDs) prepared in example 1 have good stability.
Experimental example 3 detection of Folic acid from SQDs prepared in example 1
Example 1 a sulfur quantum dot prepared by a method for detecting folic acid, the method comprising:
(1) Determination of optimal reaction conditions in the system for detecting FA concentration by SQDs:
a buffer solution (acetic acid-sodium acetate buffer) and a 1 mfa solution (prepared by dissolving FA in an aqueous sodium hydroxide solution) were prepared at pH =3 to 11. 0.8mL of buffer solutions with different pH values, 0.1mLSQDs and 0.1mLFA solutions are added into a 2mL polyethylene plastic tube, mixed uniformly, poured into a quartz cuvette after being subjected to thermostatic water bath at 25 ℃ for 1min, and the fluorescence emission peak at 450nm is measured to determine the optimum reaction pH for detecting FA.
As shown in FIG. 13, the SQDs prepared in example 1 examined pH optimization of FA. As is clear from FIG. 13, the pH of the optimum reaction for detecting folic acid was 7 to 11.
0.8mL of the buffer solution with the optimum pH (pH of 11) determined by the experiment, 0.1mLSQDs and 0.1mLFA solution are added into a 2mL polyethylene plastic tube, mixed uniformly, poured into a quartz cuvette after being respectively subjected to constant temperature water bath for 1-10 min, measured and measured for the fluorescence intensity at 450nm, and the optimum reaction time is determined according to the result.
As shown in FIG. 14, the SQDs prepared in example 1 detected the time-optimized graph of FA. As can be seen from FIG. 14, the detection reaction time was substantially stable from 1 to 10 min.
(2) Specific experiment for detecting FA by using SQDs as fluorescent probe
Selecting other substances (folic acid, starch, magnesium stearate, lactose, low-substituted hydroxypropyl cellulose, microcrystalline cellulose, cysteine, ascorbic acid and the like) in the substances to be detected for specificity test, and constructing a 1mL system: 0.9mL of SQDs +0.1mL of substances to be detected and 5mM of substances to be detected are subjected to fluorescence detection, the results are compared, and substances with specificity (folic acid) are selected to further determine the detection limit to establish a standard curve.
As shown in FIG. 15, the SQDs prepared in example 1 detected the fluorescence specificity of FA. As shown in FIG. 11, only folic acid quenches the fluorescence intensity of SQDs, and therefore, folic Acid (FA) can be detected with high specificity by this fluorescence property.
As shown in FIG. 16, the SQDs prepared in example 1 detected the fluorescence spectrum of FA. From FIG. 16, it can be seen that the fluorescence intensity corresponding to SQDs gradually decreases as the amount of folic acid added increases.
(3) SQDs as fluorescent probe to detect FA and establish standard curve
Under optimal reaction conditions (pH = 11), different concentrations of FA were added to SQDs, and the fluorescence intensity F of the reaction solution was measured at 450 nm.
As shown in FIG. 17, the SQDs prepared in example 1 were examined for the standard graph of FA. Wherein the FA concentration is plotted on the abscissa, and the fluorescence intensity F 0 /F(F 0 : sample group after addition of folic acid, F: blank group without folic acid) as ordinate, a standard curve for detecting FA was obtained. As can be seen from FIG. 17, the ratio of the concentration of folic acid to the fluorescence intensity before and after folic acid addition has a good linear relationship within the range of 10-350. Mu.M, with the detection limit being as low as 9.16. Mu.M.
Experimental example 4 evaluation of applicability of SQDs detecting folic acid method prepared in example 1
In order to evaluate the applicability of the folic acid detection method provided by experimental example 3 of the present invention, folic acid in actual drug samples was recovered by labeling. The invention detects the concentration of folic acid drugs with different brands, different auxiliary materials and specifications under the optimal conditions of various parameters (pH is 7-11, reaction time is 1-10 min). The results are shown in table 1:
table 1 shows the results of the standard recovery method for determining the folic acid content in the actual drug product, and the recovery rate of folic acid is between 96.19% and 106.25%. The results show that the method can be used for measuring the folic acid in the actual sample, and has a lower and wider concentration range than the concentration range of the folic acid detected by quantum dots reported in the existing literature.
Experimental example 5 research on the mimic oxidase Activity of SQDs prepared in example 1
The mimic oxidase activity studies were performed on the (SQDs) prepared in example 1: the optimal conditions for simulating the enzyme activity of the material were explored, and a 2mL reaction system (1.8 mL of 0.1M acetate-sodium acetate buffer, 0.1mLSQDs, and 0.1mL of 5mM TMB) was set up with TMB as the chromogenic substrate. A single variable was set to determine the optimum pH (pH 3, determined by the 652nm absorbance) for the enzymatic activity of the material at room temperature, and then the optimum temperature (40 ℃, determined by the 652nm absorbance at different temperatures) at the optimum pH. Obtaining the optimal conditions for the enzymatic reaction. The enzymatic kinetics were tested under optimal reaction temperature and pH conditions. The apparent kinetic parameters were determined according to the Michaelis-Menten equation:
V＝V max *[S]/(K m +[S])
where V is the initial velocity, V max For the maximum reaction rate, [ S ]]As substrate concentration, K m Is the Michaelis constant.
As shown in FIG. 18, a graph of the simulated oxidative enzymatic optima of SQDs prepared in example 1, wherein A is the relative activity measured at different pH values; b is the relative activity measured at different temperatures. FIG. 18 shows that the enzyme activity optimum pH of SQDs mimic oxidase is 3, and the optimum temperature is 40 ℃.
Experimental example 6 evaluation of bacteriostatic ability of SQDs prepared in example 1
Sulfur Quantum Dots (SQDs) prepared in example 1 were used for inhibiting the growth of drug-resistant bacteria and evaluating the bacteriostatic ability, the method comprising:
(1) Preparation of bacterial liquid
Transferring the drug-resistant bacteria inoculated on LB agar plate to LB broth, standing for shaking culture for 12h, diluting with sterile double distilled water, and diluting at 600nm to optical density of 0.1 (OD) 600 ＝0.1)。
(2) Minimum Inhibitory Concentration (MIC) determination of SQDs
MIC was determined by broth dilution method, and 10mg/mL, 1.0mg/mL, 10mg/mL were added to well 1 to well 7 in this order -1 mg/mL、10 -2 mg/mL、10 -3 mg/mL、10 -4 mg/mL、10 -5 100 mu L of SQDs at mg/mL, then 100 mu L of the bacterial suspension with the concentration is added into each well, a 200 mu L system is established, the mixture is mixed evenly, and each concentration is performed in three groups in parallel. 200 mu L of culture medium is used as a blank control, 100 mu L of bacterial liquid and 100 mu L of culture medium are used as positive controls, and 100 mu L of culture medium and 100 mu LSQDs are used as material color controls. And (3) placing the 96-well plate on a micro-oscillator to shake for a little time, so that the liquid in the 96-well plate is fully and uniformly mixed, and placing the 96-well plate into a constant-temperature incubator at 37 ℃ for culturing for 24 hours. OD determination by means of a microplate reader 600 And (4) judging the value, and taking the minimum concentration of the medicament which can inhibit the growth of pathogenic bacteria in the culture medium in vitro culture as MIC.
As shown in FIG. 19, the bacterial survival rate of the SQDs materials with different concentrations acted on two drug-resistant bacteria is shown in the graph, wherein A is the survival percentage of methicillin-resistant Staphylococcus aureus; b is the survival percentage of the multidrug-resistant Escherichia coli. FIG. 19 shows that the concentration of the material is less than or equal to 0.1mg/mL, and the growth of the drug-resistant bacteria can be effectively inhibited.
(3) Evaluation of antibacterial Activity of SQDs
The antibacterial activity of SQDs was evaluated using multidrug resistant Escherichia coli and methicillin resistant Staphylococcus aureus as models. Dividing multidrug-resistant Escherichia coli/methicillin-resistant Staphylococcus aureus into 2 groups (1) 100 μ L bacterial liquid and 100 μ L normal saline (CK); (2) 100. Mu.L of bacterial suspension + 100. Mu.L of LSQDs. Each group of treated bacterial suspensions was incubated at 37 ℃ for 6h to determine the optical density (OD at 600 nm) 600 )。
As shown in FIG. 20, the OD of the bacterial suspension after the treatment of different material groups 600 The value is obtained. OD 600 Indicating the optical density value of the bacteria, i.e. in absorptionAt 600nm, the greater the density of bacteria, the corresponding OD 600 The larger the value; the smaller the opposite. As seen from FIG. 20, the optical density values after SQDs treatment were greatly decreased.
And (3) further detecting the bacteriostatic activity of the SQDs by using a plate counting method by taking a culture medium without any bacteria as a background: and (3) coating each group of multi-drug resistant escherichia coli/methicillin-resistant staphylococcus aureus bacterial suspension on a solid culture medium, culturing for 12-16 h at 37 ℃, and measuring the relative viability of the bacteria by observing and counting the number of colonies.
FIG. 21 is a drawing of a petri dish after treatment of different material groups, wherein A is multi-drug resistant Escherichia coli and C is multi-drug resistant Escherichia coli + SQDs; b is multidrug-resistant Escherichia coli, and D is methicillin-resistant Staphylococcus aureus + SQDs. It is evident from FIG. 21 that SQDs have excellent bacteriostatic effects against both drug-resistant bacteria.
As can be seen from the results of FIGS. 19 to 21, the SODs have a very good inhibitory effect on the growth of both drug-resistant bacteria.
Experimental example 7 measurement of fluorescence quantum yield of SQDs prepared in example 1
The fluorescence Quantum Yield (QY) of the sulfur quantum dots SQDs prepared in example 1 was determined using quinine sulfate dissolved in 0.1M sulfuric acid as a reference (excitation at 360nm wavelength, QY of 0.546). The OD values of quinine sulfate and the sample were measured on a water basis, noting that the OD value was less than 0.05; fluorescence spectra of quinine sulfate and SQDs solutions were obtained at 360nm wavelength, and then the QY of SQDs was calculated by the following formula:
wherein Q represents the fluorescence quantum yield, I represents the integral area of the fluorescence emission peak, OD represents the ultraviolet absorption value (the limit OD is less than 0.05), n represents the refractive index of the solution, and 1 is taken; the subscript R represents the quinine sulfate reference and x represents the SQDs of the samples tested.
The incoming data is obtained:
as shown in FIG. 22, the fluorescence of SQDs prepared in example 1 is plotted against quinine sulfate. From fig. 22, the light induced quantum yield of SQD prepared in example 1 was 35.24% from quinine sulfate as a reference solution.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. Various modifications and alterations to this invention will become apparent to those skilled in the art upon reading the foregoing description. Accordingly, the scope of the invention should be limited only by the attached claims.
Claims (10)
1. A method for preparing sulfur quantum dots with high fluorescence quantum yield and simulated oxidase activity is characterized by comprising the following steps:
(1) Mixing sublimed sulfur, sodium hydroxide, polyethylene glycol 400 and water, and heating and refluxing to obtain a solution A;
(2) Mixing the solution A prepared in the step (1) with ferrate, and reacting at the same temperature as the step (1) to prepare solution B;
(3) Taking supernatant of the solution B prepared in the step (2), and recording the supernatant as solution C;
(4) Mixing the solution C obtained in the step (2) with H 2 O 2 And mixing at room temperature, and etching by hydrogen peroxide to generate sulfur quantum dots with high fluorescence quantum yield and simulated oxidase activity, which are marked as SQDs.
2. The method for preparing sulfur quantum dots with high fluorescence quantum yield and mimic oxidase activity according to claim 1, wherein the mass-to-volume ratio of sublimed sulfur, sodium hydroxide, polyethylene glycol 400 and water is 0.7g:2g:1.5mL:25mL; said H 2 O 2 The concentration of (b) is 1.6-6.5 mM, the solution C and H 2 O 2 Are equal in volume.
3. The method for preparing sulfur quantum dots with high fluorescence quantum yield and mimic oxidase activity according to claim 2, wherein the method comprisesH is as described above 2 O 2 Was 4mM.
4. The method for preparing sulfur quantum dots with high fluorescence quantum yield and simulated oxidase activity according to claim 1, wherein the mass ratio of sublimed sulfur to ferrate is 21.875:0.151.
5. the method for preparing sulfur quantum dots with high fluorescence quantum yield and mimic oxidase activity according to claim 1, wherein the temperature of heating reflux is 70 ℃.
6. A sulfur quantum dot produced by the production method according to any one of claims 1 to 5.
7. Use of the sulfur quantum dot of claim 6 in the preparation of an antibacterial agent for inhibiting drug-resistant escherichia coli and/or methicillin-resistant staphylococcus aureus.
8. Use of the sulfur quantum dot of claim 6 for the detection of folate in a non-diagnostic assay.
9. A method of using the sulfur quantum dot of claim 6 for the detection of folate in a non-diagnostic assay, comprising:
and adding the sulfur quantum dots into a sample to be detected, reacting at the pH of 2-11, and determining the fluorescence intensity of a reaction solution at the wavelength of 450 nm.
10. The method for detecting folic acid according to claim 9, wherein the pH is 7 to 11 and the reaction time is 1 to 10 minutes.
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| CN116814248B (en) * | 2023-06-30 | 2024-04-02 | 常州大学 | Preparation method and application of hybridization sulfur quantum dot with room temperature afterglow |
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