CN115254196B - Preparation method of glutathione-modified ferrous sulfide nanoparticle and application of glutathione-modified ferrous sulfide nanoparticle in glucose detection - Google Patents
Preparation method of glutathione-modified ferrous sulfide nanoparticle and application of glutathione-modified ferrous sulfide nanoparticle in glucose detection Download PDFInfo
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Abstract
The invention discloses a preparation method of glutathione modified ferrous sulfide nano particles and application thereof in glucose detection, comprising the following steps: s1, mixing glutathione and anhydrous ferrous chloride by taking deionized water as a solvent, adjusting the pH value of a reaction system, and stirring at normal temperature for reaction; s2, dropwise adding a sodium sulfide aqueous solution into the reaction system, and stirring at normal temperature for reaction; and S3, ultrafiltering, washing and freeze-drying the product obtained in the step S2 to obtain the glutathione modified ferrous sulfide nano particles. The ferrous sulfide nano particles (GSH-FeS NPs) prepared by the method can be used for detecting the content of glucose, and have the advantages of simple preparation method, easily obtained raw materials, high detection speed and the like.
Description
Technical Field
The invention belongs to the technical field of biological molecule detection, and particularly relates to a preparation method of glutathione modified ferrous sulfide nano particles and application of the glutathione modified ferrous sulfide nano particles in glucose detection.
Background
Glucose with chemical formula of C 12 H 12 O 6 Is an important energy material in human body, and is also a common chemical raw material and food additive. Natural glucose belongs to the D configuration and is dextrose. Glucose is extremely widely distributed, and is contained in various tissues of plants, blood of animals and natural honey. The glucose has wide application and can be used as a food additive in food; in medicine, can be used as glucose injection or as matrix for preparing multiple vitamins; in industrial production, glucose is often used as a reducing agent, e.g. in silver plating of thermos linersIs a reducing agent. The human body needs to take a certain amount of glucose every day, and the glucose releases heat through oxidation reaction to maintain normal life activities. However, the intake of glucose is closely related to life health, and excessive intake of glucose may induce diabetes, heart disease, hyperglycemia, etc. Therefore, quantitative detection of glucose is of great importance in food health, clinical medicine and industrial production.
The current methods for detecting glucose mainly comprise a colorimetry, an electrochemical method, a high performance liquid chromatography and the like, wherein: the high performance liquid chromatography sample pretreatment procedure is complicated, the instrument is expensive, and the cost is high; the electrochemical method is the most applied glucose detection technology in recent years, has the characteristics of simple operation, wide linear range and high sensitivity, but has poor selectivity on detection objects, needs special electrodes and electrochemical instruments for auxiliary detection, and has short storage period and relatively high cost.
Compared with an electrochemical method, the colorimetric method has the outstanding advantages of low cost, short color development time, obvious phenomenon, stable conditions, convenience and rapidness, no need of special electrodes and electrochemical instruments and the like, and plays an increasingly important role in the field of analysis and detection. The colorimetric chemical sensor is a simple analysis method for determining the content of a substance to be detected in a sample by using an ultraviolet-visible spectrophotometer or a photoelectric colorimeter and taking the lambert beer law as a theoretical basis. Colorimetric chemical sensors fall broadly into two categories: the visual colorimetric chemical sensor is used for finding a standard solution with the color similar to that of a sample solution by using eyes for observation, so that the content range of a substance to be detected in the sample is conveniently and rapidly determined, but the accuracy of the method is relatively low because the resolution of eyes is low and the influence of different environments is easy to occur. The other is a spectrophotometry method, the content of the substance to be detected is determined according to the lambert beer law by utilizing the absorbance of the substance at a specific wavelength, and the method has higher accuracy compared with a visual colorimetry.
The glucose oxidase method (GOX method) has the advantages of strong specificity, short detection time, environmental friendliness and small sample consumption, and is a relatively common method for measuring glucose by a colorimetric method.
Disclosure of Invention
In order to overcome the defects of the prior art, one of the purposes of the invention is to provide a preparation method of glutathione modified ferrous sulfide nano particles and application thereof in glucose detection. The invention realizes the detection of glucose, sensitivity and selectivity based on the peroxidase property by using the glutathione modified ferrous sulfide nano particles.
In order to achieve the above purpose, the present invention is realized by the following technical scheme:
in one aspect, the invention provides a method for preparing glutathione-modified ferrous sulfide nanoparticles, comprising the following steps:
s1, mixing glutathione and anhydrous ferrous chloride by taking deionized water as a solvent, adjusting the pH value of a reaction system, and stirring at normal temperature for reaction;
s2, dropwise adding a sodium sulfide aqueous solution into the reaction system, and stirring at normal temperature for reaction;
and S3, ultrafiltering, washing and freeze-drying the product obtained in the step S2 to obtain the glutathione modified ferrous sulfide nano particles.
Preferably, the particle size of the ferrous sulfide nano particles is 2.2-3.2nm.
Preferably, the feeding mole ratio of the glutathione, the ferrous chloride and the sodium sulfide is (2-4): 1: (4-8).
Further preferably, the feeding mole ratio of the glutathione, the ferrous chloride and the sodium sulfide is 4:1:8.
preferably, in the step S1, the pH of the reaction system is adjusted to 8-10, and the thiol in the glutathione is deprotonated under alkaline conditions to coordinate with ferrous particles to form a complex.
Preferably, in the step S3, the product is centrifuged for 5min at 5000-6000r/min by using an ultrafiltration tube with a molecular weight cut-off of 30k, and then subjected to ultrafiltration washing for a plurality of times by using ultrapure water adjusted to the same pH value. The particle size of the obtained ferrous sulfide nano particles is 2.2-3.2nm, and the ferrous sulfide nano particles have larger specific surface area and contact sites due to the ultra-small particle size, so that the catalytic performance of the ferrous sulfide nano particles is improved.
On the other hand, the invention also provides application of the ferrous sulfide nano-particles, and the ferrous sulfide nano-particles are applied to detection of glucose.
Preferably, the method for detecting glucose comprises:
(1) Establishing a standard curve with glucose concentration as a horizontal axis and ultraviolet absorbance as a vertical axis;
(2) 3,3', 5' -tetramethyl benzidine is used as a coloring agent and ferrous sulfide nano particles are used as a catalyst, glucose is oxidized by glucose oxidase to generate hydrogen peroxide, and then the hydrogen peroxide is catalyzed by the catalyst to generate a reduction reaction, so that a hydroxyl radical is generated to oxidize colorless 3,3', 5' -tetramethyl benzidine into blue-colored 3,3', 5' -oxidation state tetramethyl benzidine;
(3) The ultraviolet absorbance of the product at 652nm was measured, and the glucose content was determined from a standard curve.
Further preferably, the method for establishing the standard curve comprises the following steps:
preparing glucose standard solutions with gradient concentration, adding glucose oxidase into each glucose standard solution, and incubating for 30min at room temperature;
and sequentially adding acetate buffer solution, ferrous sulfide nanoparticle solution and 3,3', 5' -tetramethyl benzidine into the reaction systems, uniformly mixing, incubating for 5min at room temperature, and measuring the ultraviolet absorption spectrum in each reaction system to complete the establishment of a standard curve based on glucose concentration and ultraviolet absorbance.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method of the invention uses glutathione and anhydrous ferrous chloride as initial raw materials and deionized water as reaction medium, thereby avoiding the use of organic solvents and avoiding the risk of environmental pollution.
The preparation method can complete the reaction at room temperature, and has mild reaction condition and low cost.
The preparation method of the invention can rapidly prepare ferrous sulfide nano particles with uniform particle size distribution, and has simple process.
The ferrous sulfide nano particles (GSH-FeS NPs) prepared by the method can be used for detecting the content of glucose, and has the advantages of high detection speed and high accuracy.
Drawings
FIG. 1 is a transmission electron microscope image of ferrous sulfide nanoparticles (GSH-FeS NPs) of the present invention.
FIG. 2 is a statistical plot of particle size distribution of GSH-FeS NPs of this invention.
FIG. 3 is an EDS diagram of GSH-FeS NPs of this invention.
FIG. 4 is a graph of the ultraviolet-visible spectrum of GSH-FeS NPs of this invention.
FIG. 5 is an infrared spectrum of GSH-FeS NPs of this invention.
FIG. 6 is H 2 O 2 +TMB、TMB+FeS NPs、H 2 O 2 Ultraviolet-visible spectrum of +TMB +GSH-FeS NPs at 500-800 nm.
FIG. 7 is a graph of UV-visible spectra at 500-800nm for GSH-FeS NPs at different concentrations.
FIG. 8 is a graph of catalytic efficiency of GSH-FeS NPs of this invention at various temperatures.
FIG. 9 is a graph of catalytic efficiency of GSH-FeS NPs of this invention at different pH.
FIG. 10 shows the GSH-FeS NPs of the invention at different concentrations of H 2 O 2 The reaction rate of (2) is shown in graph one.
FIG. 11 shows the GSH-FeS NPs of the invention at different concentrations of H 2 O 2 And (2) the reaction rate is shown in graph II.
Fig. 12 is an established standard graph.
FIG. 13 is a graph showing the results of selective detection of glucose using GSH-FeS NPs.
Detailed Description
In order that those skilled in the art will better understand the technical solution of the present invention, preferred embodiments of the present invention will be described below with reference to specific examples, but the present invention should not be construed as being limited thereto, but only by way of example.
The test methods or test methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials, unless otherwise specified, are obtained from conventional commercial sources or prepared in conventional manner.
Example 1
The embodiment provides a preparation method of glutathione modified ferrous sulfide nano particles, which comprises the following steps:
s1, dissolving ligand glutathione and anhydrous ferrous chloride in deionized water, putting the mixture into a reaction flask, adding a newly prepared sodium hydroxide solution to adjust the pH value of a reaction system to be 8, and stirring the mixture at normal temperature for 0.5h;
s2, slowly dropwise adding a sodium sulfide aqueous solution into the reaction system, stirring for 2 hours at normal temperature, wherein the mass ratio of glutathione, ferrous chloride and sodium sulfide is 2:1:4, a step of;
s3, centrifuging the product obtained in the step S2 at a rotation speed of 5000r/min for 5min by using an ultrafiltration tube with a molecular weight cut-off of 30k after the reaction is finished, and performing ultrafiltration washing for three times by using ultrapure water adjusted to the same pH value;
s4, freeze-drying the purified product for 48 hours to obtain black GSH-FeS NPs powder.
TEM characterization of Cu 2 The particle size of the S quantum dots is about 2.2 nm.
Example 2
The embodiment provides a preparation method of glutathione modified ferrous sulfide nano particles, which comprises the following steps:
s1, dissolving ligand glutathione and anhydrous ferrous chloride in deionized water, putting the mixture into a reaction flask, adding a newly prepared sodium hydroxide solution to adjust the pH value of a reaction system to be 9, and stirring the mixture at normal temperature for 0.5h;
s2, slowly dropwise adding a sodium sulfide aqueous solution into the reaction system, stirring for 2 hours at normal temperature, wherein the mass ratio of substances of glutathione, ferrous chloride and sodium sulfide is 4:1:8, 8;
s3, centrifuging the product obtained in the step S2 at a rotation speed of 55000r/min for 5min by using an ultrafiltration tube with a molecular weight cut-off of 30k after the reaction is finished, and performing ultrafiltration washing for three times by using ultrapure water adjusted to the same pH value;
s4, freeze-drying the purified product for 72 hours to obtain black GSH-FeS NPs powder.
TEM characterization of Cu 2 The particle size of the S quantum dots is about 2.6 nm.
Example 3
The embodiment provides a preparation method of glutathione modified ferrous sulfide nano particles, which comprises the following steps:
s1, dissolving ligand glutathione and anhydrous ferrous chloride in deionized water, putting the mixture into a reaction flask, adding a newly prepared sodium hydroxide solution to adjust the pH value of a reaction system to be 10, and stirring the mixture at normal temperature for 0.5h;
s2, slowly dropwise adding a sodium sulfide aqueous solution into the reaction system, stirring for 2 hours at normal temperature, wherein the mass ratio of substances of glutathione, ferrous chloride and sodium sulfide is 3:1:6, preparing a base material;
s3, centrifuging the product obtained in the step S2 at 6000r/min rotation speed for 5min by using an ultrafiltration tube with the molecular weight cut-off of 30k after the reaction is finished, and performing ultrafiltration washing for three times by using ultrapure water adjusted to the same pH value;
s4, freeze-drying the purified product for 48 hours to obtain black GSH-FeS NPs powder.
TEM characterization of Cu 2 The particle size of the S quantum dots is about 3.2nm.
The invention takes ferrous sulfide nano particles (GSH-FeS NPs) prepared in the example 2 as an example, and the synthesis result and application thereof are described:
1. characterization of GSH-FeS NPs
Particle size of GSH-FeS NPs
At room temperature, GSH-FeS NPs were suspended in ethanol and water at a volume ratio of 1:1, determining the particle size of Cap-ZnS NCs by using a JEM-2100F transmission electron microscope (JEOL, japan), selecting one point for EDS test, and randomly counting the particle sizes of 30 Cap-ZnS NCs by using an image J, wherein the result is shown in figures 1, 2 and 3, so that ferrous sulfide nano particles with uniform sizes are obtained, and the EDS test proves that the ferrous sulfide nano particles contain iron elements and sulfur elements. (FIG. 1 is a transmission diagram, FIG. 2 is a statistical analysis of particle diameters of FIG. 1, FIG. 3 is an EDS diagram)
Ultraviolet spectra of GSH-FeS NPs
GSH-FeS NPs ultraviolet spectra in the 400-1000nm range were measured at room temperature using UV-2600. The lyophilized samples were tested in MIR-ATR mode and the results are shown in FIG. 4.
Infrared Spectroscopy of GSH-FeS NPs
4000-500cm was measured at room temperature using Bruker vertex 80v FTIR, germany -1 Infrared spectra of GSH-FeS NPs and GSH in the range. The lyophilized sample was tested in MIR-ATR mode, the results of which are shown in FIG. 5, 2624cm -1 The infrared peak at the site disappeared, proving that GSH coordinates with ferrous particles through sulfhydryl groups to form a precursor.
In order to more conveniently explain that the technical scheme of the invention can be used for successfully preparing the ferrous sulfide nano particles, the preferred embodiment 2 of the invention is exemplified, and the embodiments 1 and 3 are successfully synthesized, and the invention is not repeated.
2. Detection of peroxidase Activity of GSH-FeS NPs
The peroxidase activity detection of the partial GSH-FeS NPs comprises the peroxidase activity detection of the GSH-FeS NPs, the peroxidase activity detection of the GSH-FeS NPs with different concentrations, the peroxidase activity detection at different temperatures and pH values and the Michaelis constant detection.
Peroxidase Activity assay of GSH-FeS NPs
1mg of GSH-FeS NPs was first dissolved in 1mL of deionized water to obtain 1mg/mL of GSH-FeS NPs solution, 40. Mu.L was then added to a solution containing 120. Mu.L of HAc-NaAc buffer, 20. Mu.L of (10 mM) 3,3', 5' -Tetramethylbenzidine (TMB) solution, and 20. Mu.L of (10 mM) hydrogen peroxide solution, and after reacting for 5 minutes, the absorption spectrum thereof in the range of 500-800nm was measured by an ultraviolet-visible spectrophotometer. The absorption spectra at 500-800nm were measured using TMB+hydrogen peroxide, TMB+GSH-FeS NPs, GSH-FeS NPs+hydrogen peroxide as control group, and the results are shown in FIG. 6. It can be seen from the figure that hydrogen peroxide can cause TMB to turn blue under the catalysis of GSH-FeS NPs, and has a distinct ultraviolet absorption peak at 652 nm.
2. Peroxidase activity assay of GSH-FeS NPs at different concentrations
1mg of GSH-FeS NPs was first dissolved in 1mL of deionized water to give 1mg/mL of GSH-FeS NPs solution, which was then formulated as 500pm,250ppm,100ppm,50ppm,25ppm,5ppm GSH-FeS NPs solution. 40. Mu.l of each was added to a solution containing 120. Mu.l of HAc-NaAc buffer, 20. Mu.l of (10 mM) TMB solution, and 20. Mu.l of (10 mM) hydrogen peroxide solution, and after reacting for 5 minutes, the absorption spectrum thereof was measured in the range of 500-800nm by an ultraviolet-visible spectrophotometer. Deionized water was used as a blank, and the results are shown in FIG. 7. From the graph, it can be seen that as the concentration of GSH-FeS NPs increases, the absorption peak of oxTMB at 652nm is stronger.
3. Peroxidase activity assay at different temperatures and pH
1mg of GSH-FeS NPs was first dissolved in 1mL of deionized water to obtain 1mg/mL of GSH-FeS NPs solution, 40. Mu.L was then added to a solution containing 120. Mu.L of HAc-NaAc buffer solution, 20. Mu.L of (10 mM) TMB solution, 20. Mu.L of (10 mM) hydrogen peroxide solution, and after reacting for 5 minutes at different temperatures and pH conditions, the absorbance at 652nm was measured by an ultraviolet-visible spectrophotometer, and the results are shown in FIGS. 8 and 9. As can be seen from the figure, the optimum temperature and optimum pH for peroxidase activity of FeS NPs are 40℃and 4, respectively.
4. Mi's constant test
1mg of GSH-FeS NPs is firstly dissolved in 1mL of deionized water to obtain 1mg/mL of GSH-FeS NPs solution, and then hydrogen peroxide solutions with different concentrations are prepared for subsequent use. 40. Mu.l of the mixture was added to a buffer solution containing 120. Mu.l of HAc-NaAc, 20. Mu.l of (10 mM) TMB, and 20. Mu.l of (10 mM) hydrogen peroxide, and after reacting for 5 minutes, the absorbance at 652nm was measured by an ultraviolet-visible spectrophotometer to calculate the reaction rate, and the results were shown in FIGS. 10 and 11. As can be seen from the figure, the Michaelis constant of GSH-FeS NPs is an order of magnitude smaller than that of HRP, and the affinity of the substrate is higher.
3.GSH-FeS NPs for detecting glucose
The glucose detection experiment of GSH-FeS NPs comprises the detection of glucose with different concentrations by GSH-FeS NPs and the selective detection of GSH-FeS NPs glucose.
1. Establishing a standard curve: first, glucose solutions of different concentrations were prepared, then 20. Mu.l of glucose solution was taken, 10. Mu.l of glucose oxidase solution (1 mg/mL) was added thereto, incubation was performed at 37℃for 30 minutes, then a buffer solution containing 120. Mu.l of HAc-NaAc, 20. Mu.l of TMB solution (10 mM) and 20. Mu.l of GSH-FeS NPs solution were added thereto, and the reaction was performed at 37℃for 5 minutes, and the absorbance value at 652nm of each reaction system was measured by an ultraviolet-visible spectrophotometer to complete the establishment of a standard curve based on the glucose concentration and the ultraviolet absorbance, and the results are shown in FIG. 12. And determining the content of glucose by measuring the absorbance value of the sample to be detected.
Selective detection of gsh-FeS NPs glucose.
First, a solution of maltose, fructose, galactose, glutamic acid, urea and ascorbic acid was prepared at a certain concentration, then 20. Mu.l of each solution was added, 10. Mu.l of glucose oxidase solution (1 mg/mL) was added, incubated at 37℃for 30 minutes, then a buffer solution containing 120. Mu.l of HAc-NaAc, 20. Mu.l of (10 mM) TMB solution and 20. Mu.l of (1 mg/mL) GSH-FeS NPs solution were added thereto, and reacted at 37℃for 5 minutes, and the absorbance at 652nm was measured by an ultraviolet-visible spectrophotometer, and the results were shown in FIG. 13. It can be seen from the figure that the detection of glucose is not significantly affected in the presence of an interfering substance.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that the above-mentioned preferred embodiment should not be construed as limiting the invention, and the scope of the invention should be defined by the appended claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and such modifications and adaptations are intended to be comprehended within the scope of the invention.
Claims (8)
1. The application of the glutathione modified ferrous sulfide nano particles is characterized in that the ferrous sulfide nano particles are applied to the detection of glucose, and the preparation method of the ferrous sulfide nano particles comprises the following steps:
s1, mixing glutathione and anhydrous ferrous chloride by taking deionized water as a solvent, adjusting the pH value of a reaction system, and stirring at normal temperature for reaction;
s2, dropwise adding a sodium sulfide aqueous solution into the reaction system, and stirring at normal temperature for reaction;
and S3, ultrafiltering, washing and freeze-drying the product obtained in the step S2 to obtain the glutathione modified ferrous sulfide nano particles.
2. The use according to claim 1, wherein the particle size of the ferrous sulphide nanoparticles is 2.2-3.2nm.
3. The use according to claim 1, wherein the molar ratio of glutathione, ferrous chloride and sodium sulphide is (2-4): 1: (4-8).
4. The use according to claim 3, wherein the glutathione, ferrous chloride and sodium sulphide are dosed in a molar ratio of 4:1:8.
5. the use according to claim 1, wherein in step S1, the pH of the reaction system is adjusted to 8-10.
6. The use according to claim 1, wherein in step S3, the product is centrifuged for 5min at 5000-6000r/min using an ultrafiltration tube with a molecular weight cut-off of 30k, and then washed by ultrafiltration with ultrapure water adjusted to the same pH value.
7. The use according to claim 1, wherein the method of detecting glucose comprises:
(1) Establishing a standard curve with glucose concentration as a horizontal axis and ultraviolet absorbance as a vertical axis;
(2) 3,3', 5' -tetramethyl benzidine is used as a coloring agent and ferrous sulfide nano particles are used as a catalyst, glucose is oxidized by glucose oxidase to generate hydrogen peroxide, and then the hydrogen peroxide is catalyzed by the catalyst to generate a reduction reaction, so that a hydroxyl radical is generated to oxidize colorless 3,3', 5' -tetramethyl benzidine into blue-colored 3,3', 5' -oxidation state tetramethyl benzidine;
(3) The ultraviolet absorbance of the product at 652nm was measured, and the glucose content was determined from a standard curve.
8. The use according to claim 1, wherein the method of establishing the standard curve is:
preparing glucose standard solutions with gradient concentration, adding glucose oxidase into each glucose standard solution, and incubating for 30min at room temperature;
sequentially adding acetate buffer solution, ferrous sulfide nanoparticle solution and 3,3', 5' -tetramethyl benzidine into the reaction systems, uniformly mixing, and incubating for 5min at room temperature;
and measuring the ultraviolet absorption spectrum in each reaction system, and completing establishment of a standard curve based on the glucose concentration and the ultraviolet absorbance.
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