CN116120918A - Bimodal nanoprobe for detecting nitrite and preparation method and application thereof - Google Patents
Bimodal nanoprobe for detecting nitrite and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical fields of fluorescence spectrum, ultraviolet-visible absorption spectrum and the like, in particular to a bimodal nanoprobe for detecting nitrite, a preparation method and application thereof. The invention aims to provide a bimodal nano probe for detecting nitrite substances, which has high sensitivity, good selectivity and simple operation. Based on the fluorescence internal filtering effect and the oxidation-reduction reaction, the method is simple and has good selectivity and the potential of establishing a portable sensor; simultaneously, the ultraviolet-visible absorption spectrum and fluorescence spectrum technology are utilized, and the method can be used for colorimetric method and fluorescence method detection of the object to be detected, and has the advantages of rapid and simple operation, high sensitivity, good specificity, low detection limit and good repeatability.
Description
Technical Field
The invention relates to the technical fields of fluorescence spectrum, ultraviolet-visible absorption spectrum and the like, in particular to a bimodal nanoprobe for detecting nitrite, a preparation method and application thereof.
Background
Modern instrumental analysis mainly includes electrochemical, spectroscopic, chromatographic and mass spectrometry, etc. The spectroscopy is an analysis method (quantitative analysis) capable of determining the chemical composition of a substance (qualitative analysis) and determining the content of the substance, and can be classified into atomic spectroscopy and molecular spectroscopy according to electromagnetic radiation. The atomic spectrometry mainly comprises an atomic absorption spectrometry and an atomic emission spectrometry, and the atomic absorption spectrometry, also called atomic spectrophotometry, is an instrument analysis method for qualitatively and quantitatively analyzing an element to be detected based on the characteristic absorption spectral line of the atomic vapor of the element to be detected or the degree to which the spectral line is weakened. Atomic emission spectrometry is an analytical method for determining the composition and content of a substance element by comparing a characteristic spectrum emitted by an atom or an ion excited with a standard spectrum. The molecular spectrometry mainly comprises ultraviolet-visible absorption spectrometry, infrared spectrometry, molecular fluorescence spectrometry, molecular phosphorescence spectrometry, nuclear magnetic resonance and paramagnetic resonance spectrometry, surface enhanced Raman scattering method and the like. The spectrometry has the advantages of high analysis speed, simple operation, high sensitivity and the like, and is widely applied to the fields of industrial analysis, food inspection, environmental protection, biosensing and the like. The fluorescence spectrometry and the ultraviolet-visible absorption spectrometry have the advantages of high sensitivity, good selectivity, wide linear range, simplicity and convenience in operation and the like, and a sensor for detecting various substances can be constructed by inducing signal mechanisms such as absorbance or fluorescence intensity change and the like according to the properties of an object to be detected. Fluorescence sensing mechanisms include fluorescence quenching, enhancement, off-on, on-off, ratio, anisotropy, fluorescence resonance energy transfer, photoinduced electron transfer, and metal-enhanced fluorescence, among others. Common fluorescence quenching modes are static quenching, dynamic quenching, internal filtering effect and fluorescence quenching caused by fluorescence resonance energy transfer. The internal filtering effect is a non-radiative energy transfer, among other things, due to the quencher absorbing the excitation or emission light of the phosphor when its absorption spectrum overlaps with the excitation or emission spectrum of the phosphor.
20. Since the 90 s of century, nanotechnology has rapidly evolved and is widely used in the biosensing field. Because the nano material has unique physicochemical properties such as surface and interface effects, small-size effects, quantum size effects, macroscopic quantum tunneling effects, dielectric confinement effects and the like, the properties have great significance for the development of the biosensing field. Heretofore, various analytical methods for nitrite detection have been developed, including electrochemical methods, capillary electrophoresis, chromatography, redox titration, chemiluminescence, and the like. However, these techniques mostly require expensive instruments, time consuming and cumbersome procedures, which limit their practical application. In contrast, the fluorescence method has the advantages of low cost, high reaction speed, low detection limit, high sensitivity and specificity, and the like. The colorimetric method has the advantages of simplicity, rapidness, high sensitivity and the like, and is widely applied to the determination of micro-components. However, most probes are poorly stable, have low sensitivity, are complex to synthesize, or can only be used in a single method assay. Therefore, there is a need to design a low cost, simple bimodal nitrite detection method. The luminescent nano material mainly comprises semiconductor quantum dots, carbon dots, metal nanoclusters, up-conversion nano materials and the like. The silicon element is the element with the second position on the earth. Because of high silicon element reserve and low cost, the silicon quantum dot has been widely used as a raw material for synthesizing silicon quantum dots. The silicon quantum dot has the characteristics of excellent biocompatibility, strong light stability, low toxicity, good water solubility and the like, and can be applied to the fields of bioluminescence imaging, disease treatment, nano sensing and the like. The synthesis method of the silicon quantum dots is various, such as a microwave synthesis method, an electrochemical etching silicon wafer, a hydrothermal synthesis method and the like, and is expected to further play a significant role in the field of food analysis.
Disclosure of Invention
The invention aims to provide a bimodal nano probe for detecting nitrite substances, which has high sensitivity, good selectivity and simple operation.
The technical scheme of the invention is as follows:
a preparation method of a bimodal nanoprobe for detecting nitrite comprises the following steps:
(1) Preparing fluorescent silicon quantum dots according to the existing method;
(2) Constructing a bimodal nanoprobe according to fluorescence quenching efficiency of the phenanthrene-iron (II) o-dinitrogen complex to the silicon quantum dots;
(3) The detection of nitrite substances is realized by utilizing fluorescence spectrum and ultraviolet-visible absorption spectrum technology.
Preferably, the process of the step (1) is as follows: and mixing N- (2-aminoethyl) -3-aminopropyl trimethoxysilane and dopamine hydrochloride to prepare the silicon quantum dot solution.
Further, the specific process comprises the following steps: mixing and stirring an aqueous solution of N- (2-aminoethyl) -3-aminopropyl trimethoxysilane and a newly prepared dopamine hydrochloride solution for more than 1 hour at room temperature, and preparing the silicon quantum dot solution after dialysis and purification.
Preferably, the process of the step (2) is as follows: according to Fe 2+ Coordination ratio with phenanthroline is 1:4, and Fe with different amounts is used 2+ Preparation of phenanthrene-Fe with different concentrations from phenanthrene solution 2+ A complex; then adding the silicon quantum dot solution diluted by ultrapure water, uniformly mixing, and recording a fluorescence spectrum; the proportion of the silicon quantum dot/phenanthroline/Fe when the fluorescence intensity reaches the lowest stability 2+ Composition of the nanoprobe.
The invention also aims to protect the bimodal nanoprobe prepared by the method.
The invention also aims to protect the application of the bimodal nanoprobe in detecting the nitrite content.
Further, fluorescence: linear range 0.1-1 mM detection limit: 15.3 Mu M; ultraviolet visible absorption spectrometry: linear range 0.01-0.35mM detection limit: 18.6 Mu M.
The experimental process for detecting nitrite by using a fluorescence method and a colorimetric method comprises the following steps: fe is added to 2+ The solution, diluted hydrochloric acid and sodium nitrite standard solutions with different concentrations are uniformly mixed, after reaction and standing, phenanthrene solution and silicon quantum dot solution are respectively added, and the solution is diluted to the same volume by ultrapure water. After the reaction was allowed to stand, fluorescence spectra and ultraviolet-visible absorption spectra were recorded, respectively. And drawing a standard curve to obtain the concentration of nitrite in the sample to be detected.
The invention has the beneficial effects that:
(1) The nano probe constructed by the invention simultaneously utilizes ultraviolet-visible absorption spectrum and fluorescence spectrum technology, can be simultaneously used for colorimetric method and fluorescence method detection of an object to be detected, has the advantages of rapid and simple operation, high sensitivity, good specificity, low detection limit and good repeatability; fluorescence normal range of the application is 0.1-1 mM detection limit: 15.3 μΜ (S/n=3); ultraviolet visible absorption spectrometry: linear range 0.01-0.35mM limit of detection: 18.6 Mu M.
(2) The silicon quantum dots are used as fluorescent materials, and have good luminous stability and high fluorescent quantum yield.
(3) The principle of the construction of the nano probe is based on fluorescence internal filtration effect and oxidation-reduction reaction, and the method is simple and has good selectivity and the potential of establishing a portable sensor. The probe has wide fluorescence normal range, low detection limit, suitability for nitrite to be detected with wider concentration range and high fluorescence detection speed; the ultraviolet-visible absorption spectrometry has the performance of colorimetric and visualization, and has the potential of developing portable sensing devices.
Drawings
FIG. 1 is a schematic diagram of the detection mechanism of the present application;
FIG. 2 is a graph of fluorescence intensity versus nitrite;
FIG. 3 is a graph of fluorescence intensity versus nitrite operation;
FIG. 4 is an absorption spectrum of UV visible absorption intensity versus nitrite;
FIG. 5 is a graph of UV visible absorption intensity versus nitrite operation;
FIG. 6 is a graph showing the selectivity and interference results of the probe fluorescence method;
FIG. 7 shows the selectivity and interference of the UV-visible absorption spectroscopy.
Detailed Description
Example 1 (determination of nitrite in aqueous solution)
A preparation method of a bimodal nanoprobe for detecting nitrite comprises the following steps:
(1) Fluorescent silicon quantum dot preparation: and mixing N- (2-aminoethyl) -3-aminopropyl trimethoxysilane and dopamine hydrochloride at room temperature, and preparing the silicon quantum dot by a one-pot method. Briefly, 4.56 mL of N- (2-aminoethyl) -3-aminopropyl trimethoxysilane was slowly added to 4.44 mL ultrapure water. Then mixing the newly prepared 10 mM dopamine hydrochloride solution of 1 mL with the solution system, stirring, and changing the color of the solution from colorless to chocolate yellow, thereby indicating the synthesis of the silicon quantum dot. The solution was purified by dialysis against a dialysis bag (1 kD) for 24 hours to remove excess N- (2-aminoethyl) -3-aminopropyl trimethoxysilane and dopamine hydrochloride.
(2) Bimodal nanoprobe construction: new preparation of 5mM ferrous ion (Fe 2+ ) Solution and 5mM phenanthroline solution. First, according to Fe 2+ Coordination ratio with phenanthroline is 1:4, and Fe with different amounts is used 2+ Preparation of phenanthrene-Fe with different concentrations from phenanthrene solution 2+ A complex. Then, 100. Mu.L of the silicon quantum dot solution was added, the solution was diluted to 2 mL with ultrapure water, and the mixture was mixed well, and fluorescence spectrum was recorded. The proportion of the silicon quantum dot/phenanthroline/Fe when the fluorescence intensity reaches the lowest stability 2+ Composition of the nanoprobe. Fe (Fe) 2+ And phenanthroline concentrations were 200 μm and 800 μm, respectively.
(3) Quantitative detection of nitrite: 60 mu L of Fe is taken out respectively 2+ After reacting the solution (5 mM), 112.5. Mu.L of dilute hydrochloric acid (100 mM) with sodium nitrite standard solutions of different concentrations for 45 min, 240. Mu.L of phenanthroline solution (5 mM) and 100. Mu.L of silicon quantum dot solution were added, and diluted to 1.5 mL with ultrapure water. After standing for 5 min, the fluorescence spectrum was measured at an excitation wavelength of 380 nm. The same processing steps are adopted before the ultraviolet-visible absorption spectrometry is carried out, and a standard curve is drawn. To be treatedAfter pretreatment of the sample to be detected, quantitative detection of nitrite in the sample to be detected is realized through a fluorescence spectrometry and an ultraviolet-visible absorption spectrometry.
The determination can be directly performed on the most basic aqueous solution sample; the method can be directly measured by a fluorescence spectrum technology and an ultraviolet-visible absorption spectrum technology without an additional sample pretreatment process. The results of the relevant labeling experiments are shown in Table 1.
Table 1. Analysis of nitrite in Water sample by this probe (n=3)
Example 2 (determination of nitrite in pickled vegetables)
(1) Fluorescent silicon quantum dot preparation: and mixing N- (2-aminoethyl) -3-aminopropyl trimethoxysilane and dopamine hydrochloride at room temperature, and preparing the silicon quantum dot by a one-pot method. Briefly, 4.56 mL of N- (2-aminoethyl) -3-aminopropyl trimethoxysilane was slowly added to 4.44 mL ultrapure water. Then mixing the newly prepared 10 mM dopamine hydrochloride solution of 1 mL with the solution system, stirring, and changing the color of the solution from colorless to chocolate yellow, thereby indicating the synthesis of the silicon quantum dot. The solution was purified by dialysis against a dialysis bag (1 kD) for 24 hours to remove excess N- (2-aminoethyl) -3-aminopropyl trimethoxysilane and dopamine hydrochloride.
(2) Bimodal nanoprobe construction: new preparation of 5mM ferrous ion (Fe 2+ ) Solution and 5mM phenanthroline solution. First, according to Fe 2+ Coordination ratio with phenanthroline is 1:4, and Fe with different amounts is used 2+ Preparation of phenanthrene-Fe with different concentrations from phenanthrene solution 2+ A complex. Then, 100. Mu.L of the silicon quantum dot solution was added, the solution was diluted to 2 mL with ultrapure water, and the mixture was mixed well, and fluorescence spectrum was recorded. The proportion of the silicon quantum dot/phenanthroline/Fe when the fluorescence intensity reaches the lowest stability 2+ Composition of the nanoprobe. Fe (Fe) 2+ And phenanthroline concentrations were 200 μm and 800 μm, respectively.
(3) The pretreatment of the sample is carried out according to the pretreatment method of vegetables in the national standard GB 5009.33-2016. Then, the nitrite content was measured by fluorescence spectroscopy and ultraviolet-visible absorption spectroscopy. The results of the relevant labeling experiments are shown in Table 2.
Table 2. Analysis of nitrite in salted vegetable samples by this probe (n=3)
Example 3 (determination of nitrite in sausage)
(1) Fluorescent silicon quantum dot preparation: and mixing N- (2-aminoethyl) -3-aminopropyl trimethoxysilane and dopamine hydrochloride at room temperature, and preparing the silicon quantum dot by a one-pot method. Briefly, 4.56 mL of N- (2-aminoethyl) -3-aminopropyl trimethoxysilane was slowly added to 4.44 mL ultrapure water. Then mixing the newly prepared 10 mM dopamine hydrochloride solution of 1 mL with the solution system, stirring, and changing the color of the solution from colorless to chocolate yellow, thereby indicating the synthesis of the silicon quantum dot. The solution was purified by dialysis against a dialysis bag (1 kD) for 24 hours to remove excess N- (2-aminoethyl) -3-aminopropyl trimethoxysilane and dopamine hydrochloride.
(2) Bimodal nanoprobe construction: new preparation of 5mM ferrous ion (Fe 2+ ) Solution and 5mM phenanthroline solution. First, according to Fe 2+ Coordination ratio with phenanthroline is 1:4, and Fe with different amounts is used 2+ Preparation of phenanthrene-Fe with different concentrations from phenanthrene solution 2+ A complex. Then, 100. Mu.L of the silicon quantum dot solution was added, the solution was diluted to 2 mL with ultrapure water, and the mixture was mixed well, and fluorescence spectrum was recorded. The proportion of the silicon quantum dot/phenanthroline/Fe when the fluorescence intensity reaches the lowest stability 2+ Composition of the nanoprobe. Fe (Fe) 2+ And phenanthroline concentrations were 200 μm and 800 μm, respectively.
(3) Pretreatment of the samples was carried out according to the pretreatment method of the pickled products in the national standard GB 5009.33-2016. Then, the nitrite content was measured by fluorescence spectroscopy and ultraviolet-visible absorption spectroscopy.
Examples of the effects
Effect example 1 linear range and limit of detection investigation of fluorescence detection
The experimental conditions are as follows: 60. mu L Fe 2+ After reacting the solution (5 mM), 112.5. Mu.L of dilute hydrochloric acid (100 mM) with sodium nitrite standard solutions of different concentrations for 45 min, 240. Mu.L of phenanthroline solution (5 mM) and 100. Mu.L of silicon quantum dot solution were added, and diluted to 1.5 mL with ultrapure water. After standing for 5 min, the fluorescence spectrum was measured at an excitation wavelength of 380 nm.
The experimental results are shown in fig. 2 and 3, from which it can be seen that the fluorescence method: linear range 0.1-1 mM detection limit: 15.3 μΜ (S/n=3).
Effect example 2 inspection of the Linear Range and detection Limit of ultraviolet visible absorption Spectrometry
The experimental conditions are as follows: 60. mu L Fe 2+ After reacting the solution (5 mM), 112.5. Mu.L of dilute hydrochloric acid (100 mM) with sodium nitrite standard solutions of different concentrations for 45 min, 240. Mu.L of phenanthroline solution (5 mM) and 100. Mu.L of silicon quantum dot solution were added, and diluted to 1.5 mL with ultrapure water. After standing for 5 min, the ultraviolet visible absorption spectrum was recorded.
The experimental results are shown in fig. 4 and 5, from which it can be seen that the ultraviolet visible absorption spectroscopy: linear range 0.01-0.35mM detection limit: 18.6 μΜ (S/n=3).
Effect example 3 analysis of the anti-interference Property of the probe
The experimental conditions are as follows: 60. mu L Fe 2+ After reacting the solution (5 mM), 112.5. Mu.L of dilute hydrochloric acid (100 mM) with nitrite solution (or blank and different interfering ions) for 45 min, 240. Mu.L of phenanthroline solution (5 mM) and 100. Mu.L of silicon quantum dot solution were added and diluted to 1.5 mL with ultrapure water. After standing for 5 min, fluorescence spectra and ultraviolet-visible absorption spectra were recorded respectively.
The results are shown in fig. 6 and 7, and it can be seen that the detection of nitrite by the method has strong anti-interference performance and good detection specificity.
Claims (7)
1. The preparation method of the bimodal nanoprobe for detecting nitrite is characterized by comprising the following steps of:
(1) Preparing fluorescent silicon quantum dots according to the existing method;
(2) Constructing a bimodal nanoprobe according to fluorescence quenching efficiency of the phenanthrene-iron (II) o-dinitrogen complex to the silicon quantum dots;
(3) The detection of nitrite substances is realized by utilizing fluorescence spectrum and ultraviolet-visible absorption spectrum technology.
2. The method according to claim 1, wherein the process of step (1) is as follows: and mixing N- (2-aminoethyl) -3-aminopropyl trimethoxysilane and dopamine hydrochloride to prepare the silicon quantum dot solution.
3. The preparation method according to claim 2, wherein the specific process is: mixing and stirring an aqueous solution of N- (2-aminoethyl) -3-aminopropyl trimethoxysilane and a newly prepared dopamine hydrochloride solution for more than 1 hour at room temperature, and preparing the silicon quantum dot solution after dialysis and purification.
4. The method according to claim 1, wherein the process of step (2) is as follows: according to Fe 2+ Coordination ratio with phenanthroline is 1:4, and Fe with different amounts is used 2+ Preparation of phenanthrene-Fe with different concentrations from phenanthrene solution 2+ A complex; then adding the silicon quantum dot solution diluted by ultrapure water, uniformly mixing, and recording a fluorescence spectrum; the proportion of the silicon quantum dot/phenanthroline/Fe when the fluorescence intensity reaches the lowest stability 2+ Composition of the nanoprobe.
5. A bimodal nanoprobe prepared by the method of any of claims 1-4.
6. The use of the bimodal nanoprobe of claim 5 for detecting nitrite content.
7. The use according to claim 6, characterized in that the fluorescence method: linear range 0.1-1 mM detection limit: 15.3 Mu M; ultraviolet visible absorption spectrometry: linear range 0.01-0.35mM detection limit: 18.6 Mu M.
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