CN107831151B - Application of rare earth fluorescent nano material modified by molybdenum-based heteropoly acid in glutathione detection - Google Patents
Application of rare earth fluorescent nano material modified by molybdenum-based heteropoly acid in glutathione detection Download PDFInfo
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Abstract
The invention discloses an application of a rare earth fluorescent nano material modified by molybdenum-based heteropoly acid in glutathione detection. The method comprises the following steps: and respectively reacting a series of glutathione solutions with standard concentration with the rare earth fluorescent nano-material modified by the molybdenum-based heteropoly acid to obtain a series of mixed liquor. Detecting the change of the fluorescence intensity of the glutathione solution under the irradiation of near infrared light, making a standard curve of fluorescence and glutathione concentration, then reacting the glutathione solution with unknown concentration with the rare earth fluorescent nano material modified by the molybdenum-based heteropoly acid to obtain a mixed solution, detecting the change of the fluorescence intensity of the mixed solution under the irradiation of the near infrared light, and comparing the change with the standard curve to obtain the concentration of the glutathione solution. The method can carry out rapid, sensitive and portable quantitative detection on the glutathione, such as: the quantitative detection of food, medicine, living body samples and the like is simple to operate, good in linear effect, low in detection limit and cost, convenient to carry of instruments, capable of realizing movable detection and the like.
Description
Technical Field
The invention belongs to the technical field of analysis and detection, and particularly relates to an application of a rare earth fluorescent nano material modified by molybdenum-based heteropoly acid in glutathione detection.
Background
The analytical detection technology is to use a specified method to test specified technical performance indexes of test gas, liquid or solid. Is suitable for quality assessment in various industry categories, such as environment, food safety, water quality and the like. Glutathione is an important biological small molecule, has strong reducibility and participates in various biological processes. At present, common glutathione analysis methods comprise Raman spectrum detection, electrochemical detection and the like. However, in the current common analysis method, the instrument is not easy to carry, and movable detection is difficult to realize.
Disclosure of Invention
The invention aims to provide an application of a rare earth fluorescent nano material modified by molybdenum-based heteropoly acid in glutathione detection.
The method for detecting the concentration of glutathione in a sample to be detected provided by the invention comprises the following steps:
1) making a standard curve:
respectively reacting a series of glutathione aqueous solutions with standard concentration with an aqueous solution of a rare earth fluorescent nano material modified by molybdyl heteropoly acid to obtain a series of reaction mixed solutions, detecting the fluorescence intensity of the reaction mixed solutions under the irradiation of near infrared light with the wavelength of 808nm-980nm, and drawing a standard curve by taking the concentration of glutathione in the glutathione aqueous solution as a horizontal coordinate and the ratio of the fluorescence intensities of two different fluorescence wavelengths as a vertical coordinate; in the ratio of the fluorescence intensities, the fluorescence intensity corresponding to one fluorescence wavelength can be changed in a forward direction or a reverse direction along with different glutathione concentrations; the fluorescence intensity corresponding to the other fluorescence wavelength does not change along with the difference of the concentration of the glutathione;
2) detecting the concentration of glutathione in a sample to be detected:
replacing the glutathione solution in the step 1) with a sample to be detected, detecting the fluorescence intensity of the reaction mixed solution according to the method in the step 1), and substituting the fluorescence intensity into the standard curve obtained in the step 1) to obtain the concentration of the glutathione in the sample to be detected.
The rare earth fluorescent nano material is selected from a fluorescent nano material doped with rare earth elements or a composite fluorescent nano material of the rare earth nano material and other materials.
In the above application or method, the fluorescent nanomaterial doped with a rare earth element is selected from at least one of fluoride salt, oxide, oxyfluoride, fluorohalide, phosphate, vanadate and tungstate formed by a doping element and a rare earth element;
the mass fraction m of the doping elements is more than 0 and less than or equal to 100 percent; more specifically 20-80% or 50-60%;
the doping element is selected from erbium (Er), holmium (Ho), thulium (Tm), ytterbium (Yb), erbium (Er), ytterbium (Yb), holmium (Ho), ytterbium (Yb), thulium (Tm), manganese (Mn), lithium (Li), zinc (Zn), chromium (Cr), lead (Pb), bismuth (Bi), lithium (Li)+) Sodium, sodium (Na)+) Potassium (K)+) Rubidium (Rb)+) Cesium (Cs)+) Beryllium (Be)2+) Magnesium (Mg)2+) Calcium (Ca)2+) Strontium (Sr)2+) Barium (Ba)2+) Boron (B)3+) Aluminum (Al)3+) Gallium (Ga)3+) Indium (In)3+) Tin (Sn)2+) Lead (Pb)2+) And ammonium (NH)4 +) At least one of;
the rare earth element is specifically selected from at least one of lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), scandium (Sc), and yttrium (Y);
the composite fluorescent nano material is obtained by compounding a rare earth nano material with other materials.
The composite fluorescent nano material is specifically a material with a core-shell structure; wherein, the rare earth nano material can be used as a core or a shell. Accordingly, the other material serves as a shell when the rare earth nanomaterial serves as a core, or serves as a core when the rare earth nanomaterial serves as a shell.
The mass ratio of the rare earth nano material to other materials is 1: 0.1-10, in particular 1: 0.27;
the rare earth nano material is in the apparent form of nano particles and/or nano rods; the diameter of the nano particles is specifically 10nm-99 nm; the length of the nano rod is specifically 15nm-20 μm; the diameter is specifically 10nm-99 nm;
the rare earth nano material is specifically a material with a core-shell structure;
the other materials are inorganic materials or organic materials; the inorganic material is specifically selected from at least one of transition metals, metal sulfides, metal oxides, metal halides, semiconductor materials, and silicates; more specifically at least one selected from the group consisting of gold, silver, manganese, iron, copper sulfide, silver sulfide, tungsten sulfide, manganese sulfide, iron sulfide, silver oxide, iron oxide, copper oxide, manganese oxide, magnesium oxide, silver bromide, ferrous iodide, cuprous iodide, manganous iodide, silicon dioxide and calcium silicate;
the organic material is specifically selected from polymers; the polymer can be at least one of polydopamine, poly 3, 4-ethylenedioxythiophene and polypyrrole;
the number average molecular weight of the polydopamine is 103-106Or 104；
The number average molecular weight of the poly 3, 4-ethylenedioxythiophene is 104-106Or 105；
The number average molecular weight of the polypyrrole is 103-106Or 105。
The molybdenum-based heteropoly acid is selected from at least one of silicomolybdic acid, phosphomolybdic acid and vanadomolybdic acid;
the rare earth fluorescent nano material modified by the molybdenum-based heteropoly acid is NaGdF modified by silicomolybdic acid4Yb, Er, silicon molybdic acid modified NaLuF4Nd and phosphomolybdic acid modified NaYF4Yb, Tm.
The concentration of glutathione in the series of standard concentration glutathione aqueous solutions is 250nM-16mM, specifically 250nM, 500nM, 1. mu.M, 2. mu.M, 4. mu.M, 8. mu.M, 16. mu.M, 32. mu.M, 64. mu.M, 125. mu.M, 250. mu.M, 500. mu.M, 1mM, 2mM, 3mM, 4mM, 5mM, 6mM, 7mM, 8mM, 9mM, 10mM, 11mM, 12mM, 13mM, 14mM, 15mM, 16 mM.
In the aqueous solution of the rare earth fluorescent nano material modified by the molybdenum-based heteropoly acid, the mass concentration of the rare earth fluorescent nano material modified by the molybdenum-based heteropoly acid is 100 mu g/mL-10mg/mL, and specifically can be 200 mu g/mL.
The volume ratio of the aqueous solution of the rare earth fluorescent nano material modified by the molybdenum-based heteropoly acid to the glutathione aqueous solution with the standard concentration is (0.125-1): 1, specifically, it may be 0.25: 1;
when the fluorescence wavelengths corresponding to the two fluorescence intensities in the ratio of the fluorescence intensities in the step 1) are determined, the meaning that the fluorescence intensity can generate a positive change along with the difference of the glutathione concentration means that the fluorescence intensity corresponding to the fluorescence wavelength can be increased along with the increase of the glutathione concentration; accordingly, the reverse change means that the fluorescence intensity corresponding to the fluorescence wavelength decreases as the concentration of glutathione increases. The ratio of the fluorescence intensity is selected as the ordinate, and compared with the method of directly selecting the fluorescence intensity as the ordinate, the detection result is more accurate and the error is smaller.
In the reaction step, the temperature is 10-40 ℃; the time is 0.5-10 min.
The rare earth nano material can be prepared by a conventional method, such as: solid phase methods, liquid phase methods, gas phase methods, and the like.
Reaction time, irradiation time, detection temperature, the molybdenum group of the reaction stepThe addition amount and the addition concentration of the rare earth fluorescent nano material modified by heteropoly acid are kept consistent, the same test environment is ensured, in addition, the glutathione solution to be tested does not need to be completely reacted with the rare earth fluorescent nano material modified by molybdenum-based heteropoly acid, but the molybdenum-based heteropoly acid on the surface of the rare earth fluorescent nano material modified by molybdenum-based heteropoly acid and the glutathione in the glutathione solution to be tested are subjected to redox reaction, so that the molybdenum-based heteropoly acid is partially reduced, and Mo is causedVAnd MoVIThe amount of the added rare earth fluorescent nano material modified by the molybdenum-based heteropoly acid is consistent due to the transition of the load and the shift.
The invention realizes the rapid, sensitive and portable quantitative detection of the glutathione by using the change of the fluorescence signal of the nano material. Specifically, the linear graph (regression coefficient R) of the fluorescence intensity value and the concentration of a series of measured glutathione solutions with known concentration2Not less than 0.99) to obtain a standard linear map. And measuring the fluorescence intensity of the glutathione solution with unknown concentration, and comparing the fluorescence intensity with a standard linear map to obtain the glutathione solution.
Compared with the prior art, the invention has the following beneficial effects:
1) the method can rapidly and sensitively carry out quantitative analysis on the component to be detected in the liquid to be detected, and provides a new analysis and test method;
2) the method has the advantages of simple materials, low price of required instruments, convenient carrying and capability of realizing low-cost, quick, sensitive and portable quantitative analysis.
3) The analysis and detection method can be used for detecting samples such as environment, food, medicines, living samples and the like.
Drawings
FIG. 1 is a silicomolybdic acid-modified NaGdF of example 14Bright field photographs of Yb, Er before and after glutathione addition.
FIG. 2 is the silicomolybdic acid modified NaGdF of example 14The fluorescence spectra of Yb and Er before and after glutathione addition.
FIG. 3 is the silicomolybdic acid modified NaGdF of example 14:Yb,EAnd r, detecting the fluorescence standard linear map of the glutathione.
FIG. 4 is a silicomolybdic acid modified NaLuF in example 24Bright field photographs of Nd before and after glutathione addition.
FIG. 5 is a silicomolybdic acid modified NaLuF in example 24Fluorescence spectrum of Nd before and after glutathione addition.
FIG. 6 is a silicomolybdic acid modified NaLuF in example 24Nd detects the fluorescence standard linear map of glutathione.
FIG. 7 is a phosphomolybdic acid modified NaYF in example 34Bright field photographs of Yb, Tm before and after glutathione addition.
FIG. 8 is a phosphomolybdic acid modified NaYF in example 34Fluorescence spectra of Yb, Tm before and after glutathione addition.
FIG. 9 is a phosphomolybdic acid modified NaYF in example 34Yb, Tm is used for detecting a fluorescence standard linear map of glutathione.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.
The nanomaterial NaGdF used in the examples described below4Yb and Er are prepared according to the following method:
1) first, 0.80mmol GdCl was added3、0.18mmol YbCl3And 0.02mmol ErCl3Adding the mixture into a 100mL three-necked bottle, and then adding 6mL oleic acid and 15mL octadecene; then under the protection of nitrogen, heating the mixed solution to 120 ℃ to completely dissolve the rare earth chloride to form a transparent clear solution, stopping heating, and cooling to room temperature;
2) thereafter, 6mL NaOH (2.5mmol) and NH were added to the clear solution4Heating the methanol solution of F (4mmol) to 80 ℃ under the protection of nitrogen to remove methanol, heating to 120 ℃ after about 30min, vacuumizing to remove water and remove oxygen; finally reacting for 1h under the nitrogen atmosphere. After the reaction is finished, naturally cooling to room temperature, and then adding a proper amount of cyclohexaneAnd ethanol, centrifuging, and removing supernatant; adding a proper amount of cyclohexane into the solid, performing ultrasonic dispersion, adding a proper amount of ethanol, and performing centrifugal separation; repeating the steps, and continuously washing with cyclohexane and ethanol for several times to obtain the nano material NaGdF4Yb and Er (nano-particles with the diameter of 10-20 nm).
The nanomaterial NaLuF used in the examples described below4Nd is prepared according to the following method:
1) first, 0.93mmol of LuCl3And 0.07mmol of NdCl3Adding the mixture into a 100mL three-necked bottle, and then adding 6mL oleic acid and 15mL octadecene; then under the protection of nitrogen, heating the mixed solution to 120 ℃ to completely dissolve the rare earth chloride to form a transparent clear solution, stopping heating, and cooling to room temperature;
2) thereafter, 6mL NaOH (2.5mmol) and NH were added to the clear solution4Heating the methanol solution of F (4mmol) to 80 ℃ under the protection of nitrogen to remove methanol, heating to 120 ℃ after about 30min, vacuumizing to remove water and remove oxygen; finally reacting for 1h under the nitrogen atmosphere. After the reaction is finished, naturally cooling to room temperature; then adding appropriate amount of cyclohexane and ethanol, centrifuging, and removing supernatant; adding a proper amount of cyclohexane into the solid, performing ultrasonic dispersion, adding a proper amount of ethanol, and performing centrifugal separation; repeating the steps, and continuously washing with cyclohexane and ethanol for several times to obtain the nano material NaLuF4Nd (nanoparticles, diameter 30-35 nm).
NaYF, a nanomaterial used in the following examples4Yb, Tm is prepared according to the following method:
1) first, 0.80mmol YCl was added3、0.19mmol YbCl3And 0.01mmol of TmCl3Adding the mixture into a 100mL three-necked bottle, and then adding 6mL oleic acid and 15mL octadecene; then under the protection of nitrogen, heating the mixed solution to 120 ℃ to completely dissolve the rare earth chloride to form a transparent clear solution, stopping heating, and cooling to room temperature;
2) thereafter, 6mL NaOH (2.5mmol) and NH were added to the clear solution4Heating the solution of F (4mmol) in methanol to 80 ℃ under the protection of nitrogen to remove methanol, after about 30min,heating to 120 ℃, vacuumizing to remove water and remove oxygen; finally reacting for 1h under the nitrogen atmosphere. After the reaction is finished, naturally cooling to room temperature, then adding a proper amount of cyclohexane and ethanol, carrying out centrifugal separation, and removing supernatant; adding a proper amount of cyclohexane into the solid, performing ultrasonic dispersion, adding a proper amount of ethanol, and performing centrifugal separation; repeating the steps, and continuously washing with cyclohexane and ethanol for several times to obtain the nano material NaYF4Yb, Tm (nanoparticles, diameter 35-40 nm).
Silicomolybdic acid modified NaGdF used in the following examples4Yb and Er are prepared according to the following method:
5mg of nano material NaGdF4Yb and Er are dispersed in a mixed solution of 2.5mL of ethanol and 22.5mL of deionized water, the temperature is raised to 70 ℃, the mixture is stabilized for 30min, and 0.012g of NaOH is added. After stirring for 20min 90. mu.L tetraethyl silicate were added and after stirring for 30s 0.5mL ethyl acetate were added. Stirring in 70 deg.C water bath for 3 hr, centrifuging, washing with deionized water and ethanol for three times to obtain silica-coated NaGdF4:Yb,Er。
5mg of silica-coated NaGdF4Yb and Er are dispersed in 5mL of deionized water, 1mL of 1M hydrochloric acid solution is added, and 0.0098g (NH) is added after stirring for 10min at room temperature4)2MoO4Continuously stirring for 30min, centrifugally separating, washing with deionized water for three times to obtain the silicomolybdic acid modified NaGdF4Yb, Er. As can be seen from FIG. 1, NaGdF modified with silicomolybdic acid4Yb and Er have good dispersibility in water solution, the appearance of the solution is light yellow, and the solution turns dark blue after glutathione is added. As can be seen from FIG. 2, NaGdF modified with silicomolybdic acid4Yb and Er have obvious fluorescence emission at 540nm and 654nm, and the fluorescence intensity at 654nm is obviously weakened after glutathione is added, so that the method can be applied to the fluorescence detection of the concentration of the glutathione aqueous solution.
Silomolybdic acid modified NaLuF used in the following examples4Nd is prepared according to the following method:
5mg of nano material NaLuF4Nd dispersed in 250 μ L CH2Cl2To the solution, 2.5mL of a solution having a concentration of 37.5mgmL was added-1Ultrasonic dispersing for 5min, and heating in water bath at 60 deg.C to obtain clear transparent solution. 22.5mL of deionized water was added, the temperature was raised to 70 ℃ and stabilized for 30min, and 0.012g of NaOH was added. After stirring for 20min 90. mu.L tetraethyl silicate were added and after stirring for 30s 0.5mL ethyl acetate were added. Continuously stirring for 3 hours in a water bath at 70 ℃, performing centrifugal separation, washing with deionized water and ethanol for three times respectively to obtain the NaLuF coated with the mesoporous silica4Nd dispersed in deionized water.
NaLuF coated with 5mg of mesoporous silica4Nd dispersed in 5mL deionized water, 1mL 1M hydrochloric acid solution added, stirring at room temperature for 10min, then 0.0098g (NH)4)2MoO4Continuously stirring for 30min, centrifugally separating, washing with deionized water for three times to obtain silicomolybdic acid modified NaLuF4Nd. As can be seen from FIG. 4, NaLuF modified with silicomolybdic acid4Nd has good dispersibility in aqueous solution, the appearance of the solution is light yellow, and the solution turns dark blue after glutathione is added. As can be seen from FIG. 5, NaLuF modified with silicomolybdic acid4Nd has obvious fluorescence emission at 860nm and 1062nm, and the fluorescence intensity at 860nm is obviously weakened after glutathione is added, so that the method can be applied to the fluorescence detection of the concentration of the glutathione aqueous solution.
Phosphomolybdic acid modified NaYF used in the following examples4Yb, Tm is prepared according to the following method:
NaYF is added4Yb, Tm solution and NOBF4Mixing and ultrasonic treating at a mass ratio of 1:1 at 20 deg.C for 5min, washing off oil-soluble ligand on surface, and respectively treating with CH2Cl2Washing with anhydrous ethanol twice, dispersing in 20% sodium phosphate water solution, adding into flask in equal volume, stirring at 30 deg.C for 60min, centrifuging, washing with deionized water for three times, dispersing in 1mL deionized water, adding 0.0196g (NH)4)2MoO4Stirring for 60min, centrifuging, washing with deionized water for three times to obtain phosphomolybdic acid modified NaYF4Yb, Tm. As can be seen from FIG. 7, NaYF modified with phosphomolybdic acid4Yb, Tm is well dispersed in an aqueous solution, the appearance of the solution is pale yellow, and the solution turns dark blue after glutathione is added. As can be seen from FIG. 8, NaYF modified with phosphomolybdic acid4Yb and Tm have obvious fluorescence emission at 470nm and 800nm, and the fluorescence intensity at 800nm after glutathione is added is obviously weakened, so the method can be applied to the fluorescence detection of the concentration of the glutathione aqueous solution.
Example 1 silicomolybdic acid modified NaGdF4Yb and Er detection concentration of glutathione aqueous solution:
1) drawing a standard curve: 200. mu.L of 250nM, 500nM, 1. mu.M, 2. mu.M, 4. mu.M, 8. mu.M, 16. mu.M, 32. mu.M, 64. mu.M, 125. mu.M, 250. mu.M, 500. mu.M, 1mM, 2mM, 3mM, 4mM, 5mM, 6mM, 7mM, 8mM, 9mM, 10mM, 11mM, 12mM, 13mM, 14mM, 15mM, 16mM aqueous glutathione solution and 800. mu.L of 200. mu.g mL/L aqueous glutathione solution, respectively-1Silicomolybdic acid modified NaLuF4Uniformly mixing Yb and Er aqueous solutions, standing at room temperature (25 ℃) for reaction for 10min, determining the fluorescence spectrum of the mixed solution under the irradiation of 980nm near infrared light, processing data to obtain a fluorescence linear graph, and obtaining a standard curve of the concentration and the fluorescence intensity of the glutathione aqueous solution, wherein the standard curve is shown in figure 3. From fig. 3, it can be seen that: the standard map has good linearity in the concentration range of 125 mu M-5mM, the correlation coefficient R reaches 0.9952, and the lowest detection limit can reach 1 mu M.
2) Detection of concentration of glutathione aqueous solution: 200. mu.L of 300. mu.M glutathione aqueous solution and 800. mu.L of 200. mu.g mL-1Silicomolybdic acid modified NaGdF4Yb and Er aqueous solutions are uniformly mixed, and after standing reaction for 10min at room temperature (25 ℃), the reaction is completed, the fluorescence spectrum of the mixed solution is measured under 980nm near-infrared light irradiation, and the fluorescence spectrum is substituted into a standard curve to obtain the accurate concentration of the glutathione aqueous solution of 297.37 mu M.
Example 2 silicomolybdic acid modified NaLuF4Nd detection of the concentration of the glutathione aqueous solution:
1) drawing a standard curve: 200. mu.L of 250nM, 500nM, 1. mu.M, 2. mu.M, 4. mu.M, 8. mu.M, 16. mu.M, 32. mu.M, 64. mu.M, 125. mu.M, 250. mu.M, 500. mu.M, 1mM, 2mM, 3mM, 4mM, 5mM, 6mM, 7mM, 8mM, 9mM, 10mM, 11mM, respectivelyGlutathione in water solution of mM, 12mM, 13mM, 14mM, 15mM and 16mM and 800. mu.L concentration of 200. mu.g mL-1Silicomolybdic acid modified NaLuF4Nd aqueous solution is uniformly mixed, the mixture is kept still at room temperature (25 ℃) for reaction for 10min, the reaction is completed, the fluorescence spectrum of the mixture is measured under the irradiation of near infrared light with the wavelength of 808nm, the data is processed to obtain a linear spectrum of fluorescence, and a standard curve of the concentration and the fluorescence intensity of the glutathione aqueous solution is obtained, as shown in figure 6. From fig. 6, it can be seen that: the standard spectrum has good linearity in the concentration range of 1mM-16mM, the correlation coefficient R reaches 0.99704, and the lowest detection limit can reach 500 nM.
2) Detection of concentration of glutathione aqueous solution: 200. mu.L of 4mM glutathione aqueous solution and 800. mu.L of 200. mu.g mL-1Silomolybdic acid modified NaLuF4Nd aqueous solution is uniformly mixed, the mixture is kept still at room temperature (25 ℃) for reaction for 10min, the reaction is completed, the fluorescence spectrum of the mixture is measured under the irradiation of near infrared light with the wavelength of 808nm, and the fluorescence spectrum is substituted into a standard curve, so that the accurate concentration of the glutathione aqueous solution is 4.13 mM.
Example 3 phosphomolybdic acid modified NaYF4Yb, Tm detection of the concentration of an aqueous glutathione solution:
1) drawing a standard curve: 200. mu.L of 250nM, 500nM, 1. mu.M, 2. mu.M, 4. mu.M, 8. mu.M, 16. mu.M, 32. mu.M, 64. mu.M, 125. mu.M, 250. mu.M, 500. mu.M, 1mM, 2mM, 3mM, 4mM, 5mM, 6mM, 7mM, 8mM, 9mM, 10mM, 11mM, 12mM, 13mM, 14mM, 15mM, 16mM aqueous glutathione solution and 800. mu.L of 200. mu.g mL/L aqueous glutathione solution, respectively-1Phosphomolybdic acid modified NaYF of (a)4Yb and Tm aqueous solutions are uniformly mixed, and are kept stand at room temperature (25 ℃) for 10min to react, the reaction is complete, the fluorescence spectrum of the mixed solution is measured under the irradiation of 980nm near infrared light, and data are processed to obtain a fluorescence linear graph, so that a standard curve of the concentration and the fluorescence intensity of the glutathione aqueous solution is obtained, as shown in figure 3. From fig. 3, it can be seen that: the standard spectrum has good linearity in the concentration range of 500nM-8 muM, the correlation coefficient R reaches 0.99865, and the lowest detection limit reaches 250 nM.
2) Detection of concentration of glutathione aqueous solution: 200. mu.L of 2. mu.M glutathione aqueous solution and 800. mu.L of 200. mu.g mL-1Phosphomolybdic acid modified NaYF4Yb and Tm aqueous solutions are uniformly mixed, and after standing reaction for 10min at room temperature (25 ℃), the reaction is complete, and the fluorescence spectrum of the mixed solution is measured under 980nm near-infrared light irradiation and substituted into a standard curve to obtain the accurate concentration of the glutathione aqueous solution of 1.95 MuM.
Claims (12)
1. A method for detecting the concentration of glutathione in a sample to be detected comprises the following steps:
1) making a standard curve:
respectively reacting a series of glutathione aqueous solutions with standard concentration with an aqueous solution of a rare earth fluorescent nano material modified by molybdyl heteropoly acid to obtain a series of reaction mixed solutions, detecting the fluorescence intensity of the reaction mixed solutions under the irradiation of near infrared light with the wavelength of 808nm-980nm, and drawing a standard curve by taking the concentration of glutathione in the glutathione aqueous solution as a horizontal coordinate and the ratio of the fluorescence intensities of two different fluorescence wavelengths as a vertical coordinate; in the ratio of the fluorescence intensities, the fluorescence intensity corresponding to one fluorescence wavelength can be changed in a forward direction or a reverse direction along with different glutathione concentrations; the fluorescence intensity corresponding to the other fluorescence wavelength does not change along with the difference of the concentration of the glutathione;
2) detecting the concentration of glutathione in a sample to be detected:
replacing the glutathione solution in the step 1) with a sample to be detected, detecting the fluorescence intensity of the reaction mixed solution according to the method in the step 1), and substituting the fluorescence intensity into the standard curve obtained in the step 1) to obtain the concentration of the glutathione in the sample to be detected.
2. The method of claim 1, wherein: the rare earth fluorescent nano material is selected from a fluorescent nano material doped with rare earth elements or a composite fluorescent nano material.
3. The method of claim 2, wherein: the fluorescent nano material doped with the rare earth element is selected from at least one of fluoride salt, oxide, oxyfluoride, fluorohalide, phosphate, vanadate and tungstate formed by the doped element and other elements;
the other element is selected from at least one of manganese, lithium, zinc, chromium, lead, bismuth, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, boron, aluminum, gallium, indium, tin and lead;
the doping element is selected from at least one of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium and yttrium.
4. The method of claim 3, wherein: the mass fraction m of the doping elements is 20-80%.
5. The method of claim 4, wherein: the mass fraction m of the doping elements is 50-60%.
6. The method of claim 2, wherein: the composite fluorescent nano material is obtained by compounding a rare earth nano material with other materials;
the composite fluorescent nano material is a material with a core-shell structure;
the mass ratio of the rare earth nano material to other materials is 1: 0.1 to 10;
the rare earth nano material is in the apparent form of nano particles or nano rods;
the other materials are inorganic materials or organic materials;
the inorganic material is selected from at least one of transition metal, metal sulfide, metal oxide, metal halide, semiconductor material and silicate;
the organic material is selected from polymers; the polymer is at least one of polydopamine, poly 3, 4-ethylenedioxythiophene and polypyrrole.
7. The method of claim 6, wherein: the mass ratio of the rare earth nano material to other materials is 1: 0.27;
the diameter of the nano-particles is 10nm-99 nm; the length of the nano rod is 15nm-20 mu m, and the diameter of the nano rod is 10nm-99 nm;
the rare earth nano material is a material with a core-shell structure;
the number average molecular weight of the polydopamine is 103-106；
The number average molecular weight of the poly 3, 4-ethylenedioxythiophene is 104-106；
The number average molecular weight of the polypyrrole is 103-106。
8. The method of claim 6, wherein: the inorganic material is at least one selected from gold, silver, manganese, iron, copper sulfide, silver sulfide, tungsten sulfide, manganese sulfide, iron sulfide, silver oxide, iron oxide, copper oxide, manganese oxide, magnesium oxide, silver bromide, ferrous iodide, cuprous iodide, manganous iodide, silicon dioxide, and calcium silicate.
9. The method according to any one of claims 1-8, wherein: the molybdenum-based heteropolyacid is selected from at least one of silicomolybdic acid, phosphomolybdic acid and vanadomolybdic acid.
10. The method according to any one of claims 1-8, wherein: the rare earth fluorescent nano material modified by the molybdenum-based heteropoly acid is NaGdF modified by silicomolybdic acid4Yb, Er, silicon molybdic acid modified NaLuF4Nd and phosphomolybdic acid modified NaYF4Yb, Tm.
11. The method according to any one of claims 1-8, wherein: in the series of glutathione aqueous solutions with standard concentration, the concentration of glutathione is 250nM-16 mM;
in the aqueous solution of the rare earth fluorescent nano material modified by the molybdenum-based heteropoly acid, the mass concentration of the rare earth fluorescent nano material modified by the molybdenum-based heteropoly acid is 100 mu g/mL-10 mg/mL.
12. The method according to any one of claims 1-8, wherein: the volume ratio of the aqueous solution of the rare earth fluorescent nano material modified by the molybdenum-based heteropoly acid to the glutathione aqueous solution with the standard concentration is (0.125-1): 1;
in the reaction step, the temperature is 10-40 ℃; the time is 0.5-10 min.
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