CN110484242B - Fluorescent probe for detecting ferric ions in water and preparation and detection methods thereof - Google Patents

Fluorescent probe for detecting ferric ions in water and preparation and detection methods thereof Download PDF

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CN110484242B
CN110484242B CN201910804793.5A CN201910804793A CN110484242B CN 110484242 B CN110484242 B CN 110484242B CN 201910804793 A CN201910804793 A CN 201910804793A CN 110484242 B CN110484242 B CN 110484242B
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fluorescent probe
solution
ferric ions
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CN110484242A (en
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肖昕
张威
罗阳
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Guizhou University
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6402—Atomic fluorescence; Laser induced fluorescence
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N2021/6443—Fluorimetric titration

Abstract

The invention discloses a fluorescent probe for detecting ferric ions in water and a preparation method and a detection method thereof, wherein the molecular formula of the probe is C60H60N40O20@C22H24N2O1(ii) a The fluorescent probe is prepared from a ten-membered cucurbituril aqueous solution and an N- (3-aminopropyl) -4- (pyrene-1-yl) butanamide aqueous solution; the identification method comprises the steps of taking the fluorescent probe solution as claimed in claim 4 as a detection reagent, adding water to be detected into the fluorescent probe solution, standing for 10-20min, performing fluorescence emission spectrometry at a fixed excitation wavelength of 332nm, and drawing a change curve of the fluorescence intensity at the excited laser wavelength; and calculating fluorescence emission spectrum intensity change values delta I under 390nm and 488nm before and after the water to be detected is added into the fluorescent probe solution according to the curve, and detecting the ferric iron in the water. The fluorescent probe can detect ferric ions in water, and has the advantages of high detection speed, high selectivity, low cost and simple operation.

Description

Fluorescent probe for detecting ferric ions in water and preparation and detection methods thereof
Technical Field
The invention relates to a reagent for detecting ferric ions in water and a preparation method and a detection method thereof, in particular to a fluorescent probe for detecting ferric ions in water and a preparation method and a detection method thereof.
Background
Iron is an essential element which cannot be lacked in all living bodies and is also a trace element required in animals and plants, and is involved in constituting various enzymes and proteins in organisms. In human, iron deficiency affects the synthesis of hemoglobin and myoglobin, and may decrease the activity of certain enzymes, resulting in hypoimmunity, mental retardation, anemia, etc. Wherein iron ions (II, III) are the main existing form of iron element. Iron ions are capable of complexing a variety of proteins, and both deficiency and excess iron ions can affect cell survival and growth. The confirmation of iron deficiency and the detection of iron ions are of great significance in the fields of life science, environmental science, chemistry and the like, so that the rapid and accurate detection of trace iron ions is important.
Currently, Fe is detected3+The method (2) is mainly an atomic spectrometry method, including an inductively coupled plasma atomic emission spectrometry (ICP-AES), an Atomic Absorption Spectrometry (AAS), an inductively coupled plasma mass spectrometry (ICP-MS) and the like. Although these methods have the advantage of high sensitivity and good selectivity, these detection methods are time consumingThe need for large-scale laboratory equipment and the complexity of the sample pretreatment process, and therefore, limit the widespread use of these detection methods. In comparison, the fluorescence detection method has attracted attention because of its simple detection method and high sensitivity. Therefore, Fe with high sensitivity was developed3+Fluorescent probes are particularly important.
Disclosure of Invention
The invention aims to provide a fluorescent probe for detecting ferric ions in water and a preparation method and a detection method thereof. The fluorescent probe can detect ferric ions in water, and has the advantages of high detection speed, high selectivity, low cost and simple operation.
The technical scheme of the invention is as follows: fluorescent probe for detecting ferric ions in water, and molecular formula of fluorescent probe is C60H60N40O20@C22H24N2O1The structural formula is as follows:
Figure BDA0002183321200000021
in the preparation method of the fluorescent probe for detecting ferric ions in water, the fluorescent probe is prepared from a decatomic cucurbituril aqueous solution and an N- (3-aminopropyl) -4- (pyrene-1-yl) butanamide aqueous solution.
The preparation method of the fluorescent probe for detecting ferric ions in water comprises the following specific steps: dissolving the ten-element cucurbituril in water to obtain a solution A; dissolving N- (3-aminopropyl) -4- (pyrene-1-yl) butanamide in water to obtain a solution B; and mixing the solution A and the solution B, controlling the molar ratio of the decatomic cucurbituril to the N- (3-aminopropyl) -4- (pyrene-1-yl) butanamide to be 1:1, and reacting at normal temperature to obtain the fluorescent probe solution.
In the preparation method of the fluorescent probe for detecting ferric ions in water, the concentration of the fluorescent probe solution is 2 × 10-5mol/L。
A method for detecting ferric ions in water, which takes the fluorescent probe solution as claimed in claim 4 as a detection reagent, adds the water to be detected into the fluorescent probe solution, stands for 10-20min, performs fluorescence emission spectrometry at a fixed excitation wavelength of 332nm, and draws a variation curve of the fluorescence intensity at the laser wavelength; and calculating fluorescence emission spectrum intensity change values delta I under 390nm and 488nm before and after the water to be detected is added into the fluorescent probe solution according to the curve, and detecting the ferric iron in the water.
According to the method for detecting ferric ions in water, if the intensity of fluorescence emission spectra corresponding to 390nm and 488nm before and after the water to be detected is added is obviously weakened, the water to be detected contains ferric ions, otherwise, the water to be detected does not contain ferric ions.
The invention has the advantages of
The fluorescent probe prepared by the invention is a novel probe and can detect ferric ions in water. The detection method has the advantages of high detection speed, low cost and simple operation because of the detection of the fluorescent probe.
In addition, in the experimental process, the fluorescent probe disclosed by the invention is found to have response only to ferric ions and silver ions in the 36 metal ions participating in the test, and the fluorescent probe disclosed by the invention has the advantage of strong selectivity. Meanwhile, the ferric ions in the water to be detected can be quantitatively detected according to different changes of fluorescence intensity, and the method has the advantage of quantitative detection.
The concentration of the product obtained by the invention is 2.0X 10-5And adding solutions containing ferric ions with different volume fractions into the mol/L fluorescent probe standard solution for detection, wherein the detection result is shown in FIG. 8. This graph can be used to produce a standard curve, see FIG. 8, calculated to give a detection limit of 5.51X 10-4mol/L where it is noted that the linear range of the ferric ion response is (2.0-220.0). times.10-5mol/L。
Drawings
FIG. 1 is a fluorescence spectrum of decatomic cucurbituril and N- (3-aminopropyl) -4- (pyrene-1-yl) butanamide. Wherein: a. b is a spectrogram obtained by preparing a series of solutions by a molar ratio method and performing data processing by using origin software; c, using a batch of prepared solution prepared by the JOB method, and using origin software to perform data processing to obtain a fluorescence spectrogram;
fig. 2 is a ten-membered cucurbituril and N- (3-aminopropyl) -4- (pyrene-1-yl) butanamide nuclear magnetic titration and inclusion pattern diagram ((i) PBA, (ii) PBA: Q [10] ═ 1: 0.25, (iii) PBA: Q [10] ═ 1: 0.50(iv) PBA: Q [10] ═ 1: 1.00, (v) PBA: Q [10] ═ 1: 1.25, (vi) PBA: Q [10] ═ 1: 1.50);
FIG. 3 is a graph showing the specific selective fluorescence of the probes of the present invention for group I metal ions;
FIG. 4 is a graph showing the specific selective fluorescence of the probes of the present invention for group II metal ions;
FIG. 5 is a fluorescence diagram showing the specificity of the probe of the present invention for a portion of transition metal ions;
FIG. 6 is a fluorescence diagram showing the specificity of the probe of the present invention for lanthanide metal ions;
FIG. 7 is a comparison of fluorescence of a first main group, a second main group, lanthanide and a portion of transition metal ion specific selection cuvette in accordance with the present invention;
FIG. 8 is a fluorescence titration spectrum curve and a curve analysis of a probe standard solution when added with solutions containing ferric ions of different concentrations;
FIG. 9 shows the detection limit of the fluorescent titration when the standard solution of the probe is added to the solution containing ferric ions.
Detailed Description
The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention.
Examples of the invention
Example 1: the fluorescent probe for detecting ferric ions in water is prepared by the following specific method:
1) dissolving ten-element cucurbituril in water to obtain a solution with a concentration of 1 × 10-4mol/L solution A,;
2) dissolving N- (3-aminopropyl) -4- (pyrene-1-yl) butanamide in water to obtain a solution with a concentration of 1 × 10-3mol/L solution B;
3) and mixing the solution A and the solution B according to a molar ratio of 1:1, mixing, and reacting at normal temperature to obtain the product with the concentration of 2 x 10- 5mol/L probe solution.
Example 2: the detection method comprises the following operations:
(1) determination of the standard curve:
taking 7 10mL volumetric flasks, adding 1.0 × 10-4After 1000 mul of the mol/L fluorescent probe solution is added, 2.00 multiplied by 10 are accurately added respectively-10 muL, 1.0 muL, 2.0 muL, 3.0 muL, 4.0 muL, 5.0 muL and 6.0 muL of mol/L ferric ion standard solution, shaking up with pH 7 secondary water solution with constant volume, standing at room temperature for 10-20min, fixing excitation wavelength 332nm for fluorescence emission spectrometry, and measuring fluorescence emission intensity of probe at 390nm (I) with ferric ion concentration as abscissa0) And drawing a standard curve by taking the difference value (delta I) of the fluorescence emission intensity (I) of the ferric ions with different concentrations as a vertical coordinate. From the slope of the standard curve and the standard deviation of the blank value of 10 times, the detection limit of the fluorescent probe for detecting the ferric ions is calculated, and is shown in figure 9.
(2) Sample detection:
taking an aqueous solution containing ferric ions but with unknown concentration, adding the prepared fluorescent probe standard solution into the aqueous solution, and controlling the concentration of the aqueous solution not to exceed the linear range of (2.0-220.0) x 10-5And mol/L, and under the excitation wavelength of 332nm, observing that the fluorescence intensity at 390nm is reduced, and then indicating that the water sample contains ferric ions.
The above description is only for the purpose of illustrating the present invention and the appended claims, and the scope of the present invention is not limited thereto, and any person skilled in the art can substitute or change the technical solution and the inventive concept of the present invention within the technical scope of the present invention.

Claims (6)

1. A fluorescent probe for detecting ferric ions in water is characterized in that: molecular formula C60H60N40O20@C22H24N2O1The structural formula is as follows:
Figure FDA0002183321190000011
2. the method for preparing a fluorescent probe for detecting ferric ions in water according to claim 1, wherein the method comprises the following steps: the fluorescent probe is prepared from a ten-membered cucurbituril aqueous solution and an N- (3-aminopropyl) -4- (pyrene-1-yl) butanamide aqueous solution.
3. The method for preparing a fluorescent probe for detecting ferric ions in water according to claim 2, wherein the method comprises the following steps: the preparation method comprises the following steps: dissolving the ten-element cucurbituril in water to obtain a solution A; dissolving N- (3-aminopropyl) -4- (pyrene-1-yl) butanamide in water to obtain a solution B; and mixing the solution A and the solution B, controlling the molar ratio of the decatomic cucurbituril to the N- (3-aminopropyl) -4- (pyrene-1-yl) butanamide to be 1:1, and reacting at normal temperature to obtain the fluorescent probe solution.
4. The method for preparing a fluorescent probe for detecting ferric ions in water according to claim 3, wherein the method comprises the following steps: the concentration of the fluorescent probe solution is 2 multiplied by 10-5mol/L。
5. A method for detecting ferric ions in water is characterized in that: taking the fluorescent probe solution as claimed in claim 4 as a detection reagent, adding water to be detected into the fluorescent probe solution, standing for 10-20min, performing fluorescence emission spectrometry at a fixed excitation wavelength of 332nm, and drawing a change curve of the fluorescence intensity at the excited laser wavelength; and calculating fluorescence emission spectrum intensity change values delta I under 390nm and 488nm before and after the water to be detected is added into the fluorescent probe solution according to the curve, and detecting the ferric iron in the water.
6. The method of claim 5, wherein the method comprises: and if the intensity of the fluorescence emission spectra corresponding to 390nm and 488nm before and after the water to be detected is added is obviously weakened, indicating that the water to be detected contains ferric ions, otherwise, not containing ferric ions.
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CN114591342A (en) * 2022-04-01 2022-06-07 贵州大学 Preparation method and application of fluorescent probe for detecting Al3+ and Fe3+ in water

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