阅读说明：本技术 一种基于硅点荧光检测水产品中氟离子的方法 (Method for detecting fluorine ions in aquatic product based on silicon dot fluorescence ) 是由 叶洪丽 赵陆恺 迟海 蔡友琼 于 2021-08-16 设计创作，主要内容包括：本发明公开了一种基于硅点荧光检测水产品中氟离子的方法,属于生物分析与检测技术领域。该方法包括采用微波辅助法合成硅点,硅点加入到Fe～(3+)溶液中配制不同浓度的硅点-Fe体系,再将F～(-)离子加入到所述硅点-Fe体系中配制不同浓度的硅点-Fe-F三元络合体系,并通过荧光分析定量测定水产品中F～(-)离子。本发明基于硅点荧光检测水产品中氟离子的方法具有操作简便、反馈迅速、灵敏度和可重复性高、稳定性好和准确性强等优点,可直观地实现水样和南极磷虾等实际样品中氟离子的快速测定,为基于硅点的生物检测应用拓宽方向。(The invention discloses a method for detecting fluoride ions in an aquatic product based on silicon dot fluorescence, and belongs to the technical field of biological analysis and detection. The method comprises synthesizing silicon dots by microwave-assisted method, wherein the silicon dots are added into Fe 3+ Preparing silicon point-Fe systems with different concentrations in the solution, and adding F ‑ Ions are added into the silicon dot-Fe system to prepare silicon dot-Fe-F ternary complex systems with different concentrations, and F in the aquatic product is quantitatively determined through fluorescence analysis ‑ Ions. The method for detecting the fluorine ions in the aquatic products based on silicon dot fluorescence has the advantages of simplicity and convenience in operation, rapidness in feedback, high sensitivity and repeatability, good stability, strong accuracy and the like, can intuitively realize the rapid determination of the fluorine ions in actual samples such as water samples, antarctic krill and the like, and widens the application direction of biological detection based on silicon dots.)

1. A method for detecting fluorine ions in aquatic products based on silicon spot fluorescence,it is characterized in that after silicon dots are synthesized by adopting a microwave-assisted method, silicon dot-Fe systems with different concentrations are prepared, and F is added^-Ions are added into the silicon dot-Fe system to obtain silicon dot-Fe-F ternary complex systems with different concentrations, and F in the aquatic product is quantitatively determined through fluorescence analysis^-Ion, comprising the steps of:

(1) adding a reducing agent sodium citrate into solvent glycerol, wherein the dosage ratio of the sodium citrate to the glycerol is 0.3168: 8(W/V), magnetically stirring for 10-15min to fully dissolve the sodium citrate to obtain uniform mixed liquor;

(2) introducing argon into the mixed solution for 5-10min to remove oxygen in the solution, adding 3mL of 3- [ 2-aminoethylamino ] propyl trimethoxy silane, and continuing stirring for 5-10min under the condition of introducing argon;

(3) transferring the solution into a microwave reactor, and reacting at 160-200 ℃ for 5-15min to obtain a silicon dot solution;

(4) dialyzing the supernatant of the silicon dot solution by using a dialysis bag to obtain a pure silicon quantum dot solution, and freeze-drying;

(5) adding silicon dots to Fe³⁺The solution and the buffer solution have constant volume and are prepared into silicon point-Fe with different concentrations³⁺A solution system;

(6) adding silicon dots to Fe³⁺Standing the solution for 10-20min, adding F^-The ionic solution and the buffer solution have constant volume and are prepared into silicon point-Fe-F ternary complex solution systems with different concentrations.

2. The method for detecting fluorine ions in aquatic products based on silicon dot fluorescence according to claim 1, wherein in the step (4), the molecular cut-off amount of the dialysis bag is 1000.

3. The method for detecting fluoride ions in aquatic products based on silicon dot fluorescence as claimed in claim 1, wherein in step (5), the silicon dots are-Fe³⁺In solution system, Fe³⁺The concentration of (A) is 0.01-2 mmol/L.

4. The silicon dot-based of claim 1The method for fluorescence detection of the fluoride ions in the aquatic products is characterized in that in the step (6), F is contained in the silicon dot-Fe-F ternary complex solution system^-The concentration of (A) is 0.01-2 mmol/L.

5. Fe-containing alloy³⁺The silicon point nano fluorescent material is applied to the detection of fluorine ions.

6. Use according to claim 5, wherein the Fe-containing compound is present³⁺The silicon dot nano fluorescent material is prepared by the preparation method comprising the following steps:

(a) adding a reducing agent sodium citrate into solvent glycerol, wherein the dosage ratio of the sodium citrate to the glycerol is 0.3168: 8(W/V), magnetically stirring for 10-15min to fully dissolve the sodium citrate to obtain uniform mixed liquor;

(b) introducing argon into the mixed solution for 5-10min to remove oxygen in the solution, adding 3mL of 3- [ 2-aminoethylamino ] propyl trimethoxy silane, and continuing stirring for 5-10min under the condition of introducing argon;

(c) transferring the solution into a microwave reactor, and reacting at 160-200 ℃ for 5-15min to obtain a silicon dot solution;

(d) dialyzing the supernatant of the silicon dot solution by using a dialysis bag to obtain a pure silicon quantum dot solution, and freeze-drying;

(e) adding Si dots into Fe with concentration of 0.01-2 mmol/L³⁺The solution and the buffer solution are obtained by constant volume.

7. The use of claim 5, wherein the fluoride ions are derived from a body of aquaculture water or a water product.

Technical Field

The invention belongs to the technical field of biological analysis and detection, and particularly relates to a method for detecting fluorine ions in an aquatic product based on silicon spot fluorescence.

Background

Fluoride ion (F)^-) Is one of the elements widely existing in the human body and nature, and has a high level F^-Can damage aquatic organisms and plants, and can cause many human health problems including dental health, bone qualityOsteoporosis, acute gastric ulcer, and the like. F^-The content is an important index for the safety or pollution of soil, water and food with a certain amount, so that a novel, sensitive, accurate and rapid F is established^-The content detection method has important significance.

In the prior art, F is measured^-Common methods for content include colorimetry, electrode methods and the like, but the methods have the defects of complex operation, low sensitivity, poor reproducibility and the like, and the fluorescence analysis method based on the nano material is widely researched and applied due to the advantages of low cost, rapid feedback, high sensitivity, intuition and the like, but because F is used as the basis^-The nano fluorescent material can not be directly used for F^-The proper nano material is selected to solve the problem of F^-The key problem of detection. At present, the F is realized by regulating the fluorescence intensity of silicon dots in the silicon dot nano fluorescent material by utilizing the strong interaction of F and Fe^-And (4) reporting related to ion detection.

Disclosure of Invention

In order to solve the above problems in the prior art, the main object of the present invention is to provide a method for detecting fluorine ions in aquatic products based on silicon spot fluorescence, wherein the silicon spots rapidly prepared by microwave-assisted method have good water solubility and fluorescence property, and have Fe property³⁺Fluorescence of the silicon spot is quenched in the presence of ions, and F^-The ions may bind Fe³⁺The fluorescence of the silicon dots is recovered, and the silicon dots pass through-Fe³⁺-F^-Implementation of ternary Complex System F^-High sensitivity detection of ions.

In order to achieve the purpose, the invention adopts the following technical scheme:

the method for detecting the fluorine ions in the aquatic products based on the silicon dot fluorescence provided by the invention is characterized in that after the silicon dots are synthesized by adopting a microwave-assisted method, silicon dot-Fe systems with different concentrations are prepared, and F is added^-Ions are added into the silicon dot-Fe system to obtain silicon dot-Fe-F ternary complex systems with different concentrations, and F in the aquatic product is quantitatively determined through fluorescence analysis^-Ions; specifically, the method comprises the following steps:

(1) adding a reducing agent sodium citrate into solvent glycerol, wherein the dosage ratio of the sodium citrate to the glycerol is 0.3168: 8(W/V), magnetically stirring for 10-15min to fully dissolve the sodium citrate to obtain uniform mixed liquor;

(2) introducing argon into the mixed solution for 5-10min to remove oxygen in the solution, adding 3mL of 3- [ 2-aminoethylamino ] propyl trimethoxy silane, and continuing stirring for 5-10min under the condition of introducing argon;

(3) transferring the solution into a microwave reactor, and reacting at 160-200 ℃ for 5-15min to obtain a silicon dot solution;

(4) dialyzing the supernatant of the silicon dot solution by using a dialysis bag to obtain a pure silicon quantum dot solution, and freeze-drying;

(5) adding silicon dots to Fe³⁺The solution and the buffer solution are added to the constant volume of 1.5mL to prepare silicon-point-Fe with different concentrations³⁺A solution system;

(6) adding silicon dots to Fe³⁺Standing the solution for 10-20min, adding F^-The ionic solution and the buffer solution are metered to 1.5mL to prepare silicon point-Fe-F ternary complex solution systems with different concentrations.

Preferably, in step (4), the molecular cut-off of the dialysis bag is 1000.

Preferably, in step (5), the silicon dots are-Fe³⁺In solution system, Fe³⁺The concentration of (A) is 0.01-2 mmol/L.

Preferably, in the step (6), F is in the silicon point-Fe-F ternary complex solution system^-The concentration of (A) is 0.01-2 mmol/L.

The invention also provides a Fe-containing alloy³⁺The silicon point nano fluorescent material is applied to the detection of fluorine ions.

Preferably, the Fe-containing³⁺The silicon dot nano fluorescent material is prepared by the preparation method comprising the following steps:

(a) adding a reducing agent sodium citrate into solvent glycerol, wherein the dosage ratio of the sodium citrate to the glycerol is 0.3168: 8(W/V), magnetically stirring for 10-15min to fully dissolve the sodium citrate to obtain uniform mixed liquor;

(b) introducing argon into the mixed solution for 5-10min to remove oxygen in the solution, adding 3mL of 3- [ 2-aminoethylamino ] propyl trimethoxy silane, and continuing stirring for 5-10min under the condition of introducing argon;

(c) transferring the solution into a microwave reactor, and reacting at 160-200 ℃ for 5-15min to obtain a silicon dot solution;

(d) dialyzing the supernatant of the silicon dot solution by using a dialysis bag to obtain a pure silicon quantum dot solution, and freeze-drying;

(e) adding Si dots into Fe with concentration of 0.01-2 mmol/L³⁺The solution and the buffer solution are obtained by constant volume.

Preferably, the fluoride ions are derived from aquaculture water or aquatic products.

Compared with the prior art, the invention has the beneficial effects that:

(1) the invention is based on the fluorescence quenching principle of electron transfer, and the specific selection can be carried out on Fe³⁺Producing quenched silicon-dot nanofluorescent materials using F^-Strong interaction of ions with Fe, F^-The ions may bind Fe³⁺Formation of stable FeF₃Compound (ii) of Fe³⁺The silicon spot is released from a silicon spot-Fe system, an electron transfer channel is cut off, and the fluorescence of the silicon spot is recovered, so that a silicon spot-based F measurement method is established^-The 'quenching-recovery' fluorescence analysis method of ions successfully realizes the F pair^-The high efficiency, sensitivity and rapidity of the determination.

(2) The method for detecting the fluorine ions in the aquatic products based on silicon dot fluorescence has the advantages of simplicity and convenience in operation, rapidness in feedback, high sensitivity and repeatability, good stability, strong accuracy and the like, can intuitively realize rapid determination of the fluorine ions in actual samples such as water samples and antarctic krill, and widens the direction of biological detection application based on silicon dots.

The above-described and other features, aspects, and advantages of the present invention will become more apparent with reference to the following detailed description.

Drawings

Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:

FIG. 1 is a graph of the detection F in the example^-A test schematic of (a); wherein: (A) silicon dot solution, silicon dot-Fe-F^-Emission spectrum of the solution; (B) silicon dot solution, silicon dot-Fe-F^-Corresponding fluorescence photograph of the solution in 365nm UV dark box; (C) relative fluorescence intensity and F^-Linear relationship of ion concentration.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the drawings of the embodiments of the present invention. It is to be understood that the embodiments described are only some of the embodiments of the invention, and not all of them. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention without any inventive step, are within the scope of protection of the invention.

Example 1

The embodiment provides a method for detecting fluorine ions in an aquatic product based on silicon spot fluorescence, which comprises the following steps:

1) adding a reducing agent sodium citrate into solvent glycerol, wherein the dosage ratio of the sodium citrate to the glycerol is 0.3168 g: stirring for 15min by magnetic force for 8mL to fully dissolve the sodium citrate to obtain uniform mixed liquor;

2) introducing argon into the mixed solution for 10min to remove oxygen in the solution, adding 3mL of 3- [ 2-aminoethylamino ] propyl trimethoxy silane, and continuing stirring for 10min under the condition of introducing argon;

3) transferring the solution into a microwave reactor, and reacting for 15min at 180 ℃ to obtain a silicon dot solution;

4) dialyzing the supernatant by using a dialysis bag, wherein the molecular interception amount of the dialysis bag is 1000, water is changed once every 6 hours for 4 times, and the total dialysis time is 24 hours to obtain pure silicon quantum dot solution, and freeze-drying;

5) taking a certain amount of silicon dots, adding into Fe³⁺The solution and the buffer solution are added to the constant volume of 1.5mL, and finally 10 mu mol/L Fe containing silicon dots is prepared³⁺A solution;

6) taking a certain amount of silicon dots, adding into Fe³⁺Standing the solution for 10min, adding F^-The ionic solution and the buffer solution are added to the constant volume of 1.5mL, and finally the solution is prepared to contain silicon dots and Fe³⁺10. mu. mol/L F^-And (3) solution.

Example 2

This example provides a method for detecting fluoride ions in aquatic products based on silicon spot fluorescence, which has the same steps as example 1, except that Fe in step 5)³⁺The concentration of (2) was 20. mu. mol/L.

Example 3

This example provides a method for detecting fluoride ions in aquatic products based on silicon spot fluorescence, which has the same steps as example 1, except that Fe in step 5)³⁺The concentration of (2) is 100. mu. mol/L.

Example 4

This example provides a method for detecting fluoride ions in aquatic products based on silicon spot fluorescence, which has the same steps as example 1, except that Fe in step 5)³⁺The concentration of (2) was 500. mu. mol/L.

Example 5

This example provides a method for detecting fluoride ions in aquatic products based on silicon spot fluorescence, which has the same steps as example 1, except that Fe in step 5)³⁺The concentration of (2) was 1000. mu. mol/L.

Example 6

This example provides a method for detecting fluoride ions in aquatic products based on silicon spot fluorescence, which has the same steps as example 1, except that Fe in step 5)³⁺The concentration of (2) was 2000. mu. mol/L.

Example 7

This example provides a method for detecting fluoride ions in aquatic products based on silicon spot fluorescence, which has the same steps as example 1, except that F in step 6)^-The concentration of (2) was 20. mu. mol/L.

Example 8

The embodiment provides a method for detecting fluorine ions in an aquatic product based on silicon spot fluorescence, and the steps are basically the same as those in embodiment 1With the difference that F in step 6)^-The concentration of (2) is 100. mu. mol/L.

Example 9

This example provides a method for detecting fluoride ions in aquatic products based on silicon spot fluorescence, which has the same steps as example 1, except that F in step 6)^-The concentration of (2) was 500. mu. mol/L.

Example 10

This example provides a method for detecting fluoride ions in aquatic products based on silicon spot fluorescence, which has the same steps as example 1, except that F in step 6)^-The concentration of (2) was 1000. mu. mol/L.

Example 11

This example provides a method for detecting fluoride ions in aquatic products based on silicon spot fluorescence, which has the same steps as example 1, except that F in step 6)^-The concentration of (2) was 2000. mu. mol/L.

Effect example 1

1) silicon dots, 2) silicon dots + 300. mu. mol/L Fe were prepared according to the above method³⁺3) silicon site + 300. mu. mol/L Fe³⁺+100μmol/L F^-4) silicon site + 300. mu. mol/L Fe³⁺+200μmol/L F^-5) silicon site + 300. mu. mol/L Fe³⁺+300μmol/L F^-6) silicon site + 300. mu. mol/L Fe³⁺+400μmol/L F^-7) silicon site + 300. mu. mol/L Fe³⁺+500μmol/L F^-8) silicon site + 300. mu. mol/L Fe³⁺+100μmol/L F^-Detection of F in aquatic product by using silicon dot nano fluorescent material^-The results are shown in FIG. 1, which shows the emission spectra in FIG. 1(A), the corresponding fluorescence photograph in 365nm UV dark box in FIG. 1(B) and the relative fluorescence intensity and F^-The linear relationship of the ion concentration is shown in FIG. 1(C), R²0.980 proves that the method for detecting the fluorine ions in the aquatic products based on silicon dot fluorescence has high sensitivity and repeatability, good stability and strong accuracy, and can intuitively realize the rapid determination of the fluorine ions in actual samples such as water samples, antarctic krill and the like.