CN107991273B - Hg based on imidazole derivative fluorescent probe2+And S2-Relay fluorescence detection method - Google Patents

Abstract

The invention relates to relay fluorescence detection of Hg²⁺And S^2–And (5) establishing a method. The inventionAims to solve the problem of the prior relay fluorescence detection of Hg in aqueous solution²⁺And S^2–The fluorescent probe of (2) is very few, and is used for Hg²⁺Susceptible to Au upon recognition³⁺,Fe²⁺And Fe³⁺The problem of influence. The probe of the invention is 1, 4-o-phthalic di-3- (1-pentylbenzimidazole) acetanilide chloride [ L]Can react with Hg in HEPES aqueous solution²⁺Forming a stable complex, quenching the L fluorescence; the probe can be used for Hg within a pH range of 2.0-11.3²⁺The fluorescence performance is stable; hg is a mercury vapor²⁺Can reach 4.0 x 10^–7mol/L. Compound [ L-Hg ]²⁺]Can also realize the S^2–Fluorescence detection, therefore, the probe can realize the detection of Hg in aqueous solution²⁺And S^2–The relay fluorescence detection has great application prospect in the fields of environmental science, analytical chemistry, life science and the like.

Description

Hg based on imidazole derivative fluorescent probe2+And S2-Relay fluorescence detection method

Technical Field

The invention relates to relay fluorescence detection of mercury ions (Hg)²⁺) And sulfide ion (S)^2–) And (5) establishing a method.

Background

Ion recognition has attracted considerable attention in the past decades due to its critical role in the biological, environmental and chemical fields. Although many selective fluorescent probes have been reported previously, there are relatively few multifunctional fluorescent probes that can achieve relay identification. Therefore, it is very meaningful to develop a recyclable, low-cost and high-performance relay recognition fluorescent probe.

The development of new probes that selectively recognize toxic heavy metal ions and anions has received increasing attention. 2016 Mehdi AmiAn article published by rnasr et al in Sensors and actors B, fluorescent carbon amides ligand, fluorescent conjugated ionophore/fluorescent moieties, inhibition "On-Off switching heated Zn²⁺ion "relates to Zn²⁺Detection of (3). In addition, some researchers reported some reports on Cu²⁺, Fe³⁺And Cr³⁺Isocationic detection. An article published in Inorganic Chemistry Communications by Hyun Yong Jo et al in 2015, "A colorimetric Schiff base chemosensor for CN^–by name-eye in aqueous solution relating to CN^–Detection of (3). In addition, some of the researchers reported that F is not a factor^–, AcO^–, H₂PO₄ ^–And HPO₄ ^2–Report of plasma detection. Hg is one of the most toxic heavy metal elements, since both elemental mercury and mercury ions can be converted to methyl mercury in the environment by bacteria and subsequently bioaccumulated by the food chain. It causes dysfunction of the brain, kidney, stomach and central nervous system due to its eosinophilic properties in proteins and enzymes. Hydrogen sulfide (H)₂S) is ubiquitous in the environment and in organisms, and is present predominantly in the form of S^2–And HS^–And the like. S^2–The content of the compound in human bodies is excessive, and the compound has great influence on the physiological processes of the human bodies, including the digestive system, the central nervous system, the endocrine system and the like. Therefore, how to detect Hg in an aqueous solution²⁺And S^2–The content of (b) becomes an important task for scientific research.

Identification of Hg reported at present²⁺Most of the probes are also detected in a solvent, have low selectivity and are easy to be subjected to Au³⁺、Fe²⁺And Fe³⁺The influence of (c). For example, the published RSC Advances by Ceren Canturk et al article "A BODIPY-based fluorescent reagent for the differential recognition of Hg (II) and Au (III) ions" implements the detection of Hg by fluorescent probes²⁺And Au³⁺And Hg cannot be detected singly²⁺(ii) a An article published by Kaushik Ghosh et al in Eurdic European Journal of organic Chemistry, A Simple Fluorescent Probe Derived from Naphtylamine for Selective Detection of Hg^II, Fe^II and Fe^IIIIons in Mixed Aqueous Media, Applications in Living Cells and Logic Gates, realizes the detection of Hg by fluorescent probes²⁺、Fe²⁺And Fe³⁺And Hg cannot be detected singly²⁺(ii) a The publication of high selective reproduction of hydrogen sulfide and Hg (II) by a commercial available fluorescent chemosensor and its application in biology by Yutao Yang et al in Sensors and actors B achieves the goal of addressing Hg in a mixed solution of dimethyl sulfoxide and water²⁺And HS^–Relay fluorescence detection; an article by Anefficient Hg published by Ramesh C. Gupta et al in Sensors and actors B²⁺ The implementation of the sensitive based on a three-fused precipitated anthracene and quinoline system for selective detection of cyclic fluoride turn-off-on-reaction in solution and live cell in the mixed solution of tetrahydrofuran and water²⁺And CN^–Relay fluorescence detection; an article published by Richa Goel et al in Sensors and actors B, sodium based chromofluoro sensor and DNA integrator, trigger by Hg²⁺/ HSO₄ ^–clean reaction realized by the method of treating Hg in methanol solution²⁺And HSO₄ ^–Relay fluorescence detection; a published article by Muthu Vengaian et al in Sensors and actors B, Phenothiazine-diamminenical based colorimetry and Fluorescence "Turn-off-on" Sensing of Hg²⁺ and S^2–The realization is to Hg in the mixed solution of ethanol and water²⁺And S^2–Relay fluorescence detection. The invention relates to a method for synthesizing a high-selectivity relay fluorescence detection device for Hg in an aqueous solution²⁺And S^2–The imidazole derivative fluorescent molecular probe is used for detecting Hg in aqueous solution²⁺Has stronger single selective fluorescence quenching identification, good identification effect and low detection limit. Based on Hg²⁺Probes of ion complexes with H₂After S is bound, the metal ion is bonded with S^2–Form a sinkPrecipitation (HgS), recovery of fluorescence of probe molecules, and realization of probe to Hg in aqueous solution²⁺And S^2–Relay fluorescence detection. The method has great application prospect in the fields of environmental science, analytical chemistry, life science and the like.

Disclosure of Invention

The invention aims to solve the problem of the prior relay fluorescence detection of Hg in aqueous solution²⁺And S^2–The fluorescent probe of (2) is very few, and is used for Hg^{2 +}Susceptible to Au upon recognition³⁺, Fe²⁺And Fe³⁺Influence, thereby providing an imidazole derivative Hg²⁺And S^2–Relay fluorescence detection and methods of use

The imidazole derivative fluorescent probe 1, 4-o-phthalic-3- (1-pentylbenzimidazole) acetanilide chloride [ L ] has a structural formula as follows:

testing of Hg Using the method of the invention²⁺HEPES is taken as a buffer solution, and the solvent of the buffer solution is deionized water, so that Hg can be detected singly in a high-selectivity manner²⁺Free from other metal ions (Al) in the aqueous solution³⁺, Zn²⁺, Ag⁺, Ca²⁺, Mg²⁺, Fe³⁺, Pb²⁺, Na⁺, Ba²⁺, Ni²⁺, K⁺, Cu²⁺, Cr³⁺, Cd²⁺, Co²⁺) The interference of (2) has stronger anti-interference capability. The probe can be used for Hg within the pH value range of 2.0-11.3²⁺The fluorescence property is stable. Detection limit of 4.0 × 10^–7mol/L. Based on Hg²⁺The probe of the ion complex can realize relay fluorescence detection of S in aqueous solution^2–. In conclusion, the technical effects of the invention are very obvious, and the invention provides a method for detecting Hg by high-selectivity relay fluorescence, which is environment-friendly, simple and rapid in detection operation and high in selectivity²⁺And S^2–The method of (1).

Imidazole derivatives of the inventionThe fluorescent probe can detect Hg in aqueous solution by relay fluorescence²⁺And S^2–Has extremely high application value.

Drawings

FIG. 1 is a graph showing fluorescence emission spectra of 1, 4-o-phthalic-3- (1-pentylbenzimidazole) acetanilide chloride [ L ] fluorescent probe of example 1 for different cations.

FIG. 2 is the 1, 4-o-phthalic-3- (1-pentylbenzimidazole) acetanilide chloride [ L ] of example 2]At different Hg²⁺Fluorescence spectrum change pattern at concentration.

FIG. 3 shows other common metal ions and Hg in example 3²⁺In competition, 1, 4-o-phthalic di-3- (1-pentylbenzimidazole) acetanilide chloride [ L]Fluorescence change pattern of (2).

FIG. 4 is [ L-Hg ] of example 5²⁺]Fluorescence emission spectra of the fluorescent probe for different anions.

FIG. 5 shows the addition of Hg to L in example 8²⁺And S^2–And 5 times of circulation to obtain a fluorescence intensity change graph.

Detailed Description

Example 1

HEPES buffer solution pH =7.4 was used as a solvent, and the concentration was measured to be 1.0X 10^–5Fluorescence emission spectra of the L solution in mol/L for 16 common cations. To the L solution was added 6.0 equiv. 16 kinds of cations (Al)³⁺, Zn²⁺, Ag⁺, Ca²⁺, Mg²⁺, Fe³⁺, Hg²⁺, Pb²⁺, Na⁺, Ba²⁺, Ni²⁺, K⁺, Cu²⁺, Cr³⁺, Cd²⁺, Co²⁺) Solution of only 6.0 equiv. Hg²⁺Can enable L fluorescence to be remarkably quenched, and the quenching amplitude is 83 percent. In contrast, other metal ions cause only small changes. Shows that the fluorescent probe L of the invention is opposite to Hg²⁺Has the characteristic of single-selection fluorescence detection. Wherein: the ordinate represents the fluorescence intensity and the abscissa represents the fluorescence wavelength.

Example 2

Using HEPES buffer solution with pH =7.4 as solvent, and mixing different concentrationsHg at a degree of 0 to 11.0 equiv²⁺Adding into a reactor at 1.0X 10^–5In the L solution of mol/L, the change result of the fluorescence emission spectrum is observed. With Hg²⁺The concentration increased and the fluorescence intensity of L at 370 nm gradually decreased, and the above results indicate that L is against Hg²⁺Has higher sensitivity. Wherein: the ordinate represents the fluorescence intensity and the abscissa represents the fluorescence wavelength.

Example 3

At a concentration of 1.0X 10^–5Adding 12.0 equiv. 15 kinds of cations (Al) into the L solution of mol/L³⁺, Zn^{2 +}, Ag⁺, Ca²⁺, Mg²⁺, Fe³⁺, Pb²⁺, Na⁺, Ba²⁺, Ni²⁺, K⁺, Cu²⁺, Cr³⁺, Cd²⁺, Co²⁺) Shaking the solution, standing for 5min, and adding 6.0 equiv. Hg²⁺Shaking the solution evenly. The fluorescence intensity of the 15 cations was close to that of L by adding 6.0 equiv. When the 15 cations are mixed with Hg²⁺Coexisting and the cation concentration is Hg²⁺At 2 times the concentration, L does not interfere with Hg²⁺The detection shows that the system still has obvious fluorescence quenching response, which indicates that L is applied to Hg²⁺The detection has excellent anti-interference performance and can be used for detecting Hg²⁺The fluorescence quenching probe of (1). Wherein: the ordinate represents the fluorescence intensity, the abscissa represents the metal ion species, (0) blank, (1) Al³⁺, (2) Zn²⁺, (3) Ag⁺, (4) Ca²⁺, (5) Mg²⁺, (6) Fe³⁺, (7) Pb²⁺, (8) Na⁺, (9) Ba²⁺, (10) Ni²⁺, (11) K⁺, (12) Cu²⁺, (13) Cr³⁺, (14) Cd²⁺, (15) Co²⁺。

Example 4

The concentration is 1.0X 10^–5An aqueous solution of L in mol/L and containing 6.0 equiv. Hg²⁺ The pH value of the aqueous solution L is adjusted by nitric acid or sodium hydroxide solution, and the change of the fluorescence intensity of the solution along with the pH value is measured. Comparing the two curves of the fluorescence intensity changing along with the pH value, the Hg in the pH range of 2.0-11.3 can be known²⁺Form a stable complex with L, resulting in significant quenching of solution fluorescence. Namely, the L can be used for treating Hg in a wider pH range, particularly under the condition of pH 7.35-7.45 in a physiological environment²⁺ The identification detection of (1).

Example 5

After selective quenching identification, fluorescence spectroscopy is used to study [ L-Hg ]²⁺]18 anions (I) in water (HEPES, pH = 7.4) solution^–, Cl^–, Br^–, F^–, HCO₃ ^–, CO₃ ^2–, SO₃ ^2–, HSO₃ ^–, SO₄ ^2–, NO₃ ^–, NO₂ ^–, HPO₄ ^2–, H₂PO₄ ^–, BrO₃ ^–, SCN^–, AcO^–, PO₄ ^3–, S^2–) Relay fluorescence detection capability. In the complex [ L-Hg²⁺] (1.0×10^–5mol/L) solution is added with 6.0 equiv. of the 18 anions, only 6.0 equiv. S^2–The fluorescence value of the subject L can be completely recovered. In contrast, other anions cause only minor changes. Due to S^2–Hg robbery removal²⁺A stable HgS complex is formed, resulting in the release of probe L. Apparently, the complex [ L-Hg ]²⁺]Can be used as a fluorescent probe in relay fluorescence detection and used for biological analysis. Wherein: the ordinate represents the fluorescence intensity and the abscissa represents the fluorescence wavelength.

Example 6

In HEPES buffer solution with pH =7.4, S with different concentrations (0-10.0 equiv.) is added^2–Adding into a reactor at 1.0X 10^–5mol/L of [ L-Hg ]²⁺]In the solution, the change of the fluorescence emission spectrum was observed. With S^2–Increase in concentration, [ L-Hg ]²⁺]Until 6.0 equiv. S is added^2–The fluorescence intensity returns to the fluorescence value of the subject L.

Example 7

At a concentration of 1.0X 10^–5mol/L of [ L-Hg ]²⁺]To the solution was added 12.0 equiv. anion (I)^–, Cl^–, Br^–, F^–, HCO₃ ^–, CO₃ ^2–, SO₃ ^2–, HSO₃ ^–, SO₄ ^2–, NO₃ ^–, NO₂ ^–, HPO₄ ^2–, H₂PO₄ ^–, BrO₃ ^–, SCN^–, AcO^–, PO₄ ^3–) Shaking the solution, standing for 5min, and adding 6.0 equiv. S^2–Shaking the solution evenly. When the 17 anions mentioned above are reacted with S^2–Coexisting, and the anion concentration is S^2–At 2 times of concentration, the [ L-Hg ] is not interfered²⁺]To S^2–Detection of (2) indicates [ L-Hg ]²⁺]To S^2–The detection has excellent anti-interference performance.

Example 8

At a concentration of 1.0X 10^–5mol/L of solution L, Hg²⁺And S^2–The fluorescence intensity was measured at a concentration of 6.0 equiv. Sequentially adding Hg to the L solution²⁺And S^2–And the fluorescence intensities obtained after 5 times of circulation are 247.3, 47.2, 247.0, 52.2, 238.0, 50.2, 231.1, 49.0, 222.2, 50.0 and 216.0 respectively. Indicating L to Hg²⁺The recognition is reversible. Wherein: the ordinate represents the fluorescence intensity and the abscissa represents the number of cycles.

Example 9

In HEPES buffer solution with pH =7.4, Hg with different concentrations (0-11.0 equiv.) is added²⁺Adding into a reactor at 1.0X 10^–5In the L solution of mol/L, the change of the fluorescence emission spectrum is observed. With Hg²⁺Increasing the concentration, decreasing the fluorescence intensity of L, Hg²⁺Fluorescence intensity vs. Hg at a concentration of 0-1.0. mu.M²⁺In a linear relationship, the linear equation is Y =238.1331-93.2289X (linear correlation coefficient: R)²= 0.9949); blank is assayed 20 times in parallel at 3 sigma-K(a is a blank standard deviation of the standard,Kslope of regression equation) to a detection limit of 4.0 × 10^–7mol/L. This isThe result shows that the probe L can be used for qualitatively detecting Hg with high sensitivity²⁺。

Claims (1)

1. A mercury ion and sulfur ion relay fluorescence detection method based on an imidazole derivative fluorescent probe is characterized by comprising the following steps:

HEPES buffer solution with pH 7.4 as solvent, and the concentration is 1.0 × 10^-5Fluorescence emission spectrum of the probe solution of mol/L to the solution I to be detected, if the fluorescence of the probe is quenched, Hg is contained in the solution I to be detected²⁺The complex [ L-Hg ] is formed]；Hg²⁺Fluorescence intensity vs. Hg at a concentration of 0-1.0. mu.M²⁺The linear relation is formed; detection limit of 4.0 × 10^–7mol/L；

II, in the concentration of 1.0X 10^–5mol/L complex [ L-Hg [ ]]Adding a solution II to be detected into the solution, and if the fluorescence value of the probe is recovered, determining that the solution II to be detected contains S^2–Completing Hg²⁺And S^2–Relay fluorescence detection;

the fluorescent probe is 1, 4-o-phenyl di-3- (1-amyl benzimidazole) acetanilide chloride [ L ], and the structural formula of the fluorescent probe is as follows:

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