CN113880867B

CN113880867B - Detectable Cu in water 2+ 、Zn 2+ Molecular sensor and application

Info

Publication number: CN113880867B
Application number: CN202111190528.6A
Authority: CN
Inventors: 王芳; 郭长友; 李洪亮; 朱宝勇; 徐冬梅; 何琦; 魏雪; 刘淑妍; 吕雪灵
Original assignee: Dezhou University
Current assignee: Dezhou University
Priority date: 2021-10-13
Filing date: 2021-10-13
Publication date: 2023-06-09
Anticipated expiration: 2041-10-13
Also published as: LU501426B1; CN113880867A

Abstract

The invention provides a kind of foodDetection of Cu in Water ²⁺ 、Zn ²⁺ Molecular sensor and application relate to organic function material detection technical field. The molecular sensor provided by the invention is prepared by taking 1, 7-tetramethyl-8-hydroxy-9-julolidine aldehyde and p-phenylenediamine as reaction raw materials through one-step polymerization reaction; the molecular sensor simultaneously contains three ionic action sites of rigid fatty naphthenoamine, imine and hydroxyl, and the coordination of the dual sites of imine and ortho-phenol hydroxyl has stronger coordination capability to metal ions, so that the dual sites of imine and ortho-phenol hydroxyl are coordinated to Cu ²⁺ 、Zn ²⁺ The ions show sensitive fluorescence reduction, enhance detection signals, have high sensitivity and good selectivity, and have remarkable application value; the preparation method has the advantages of high yield, simple synthesis process, easy implementation and the like, is suitable for industrial popularization, and creates favorable conditions for popularization and application of the molecular sensor.

Description

Detectable Cu in water 2+ 、Zn 2+ Molecular sensor and application

Technical Field

The invention relates to the technical field of organic material function detection, in particular to a method capable of sensitively detecting Cu in water ²⁺ 、Zn ²⁺ Molecular sensor of ion and application.

Background

With the rapid development of global economy, the pollution problem of water resources is more serious, especially the heavy metal pollution in the water resources. The heavy metal pollution has the characteristics of concealment, long-term property, accumulation property, irreversibility and the like, and the heavy metal toxicity is high and is easy to enrich and expand in a biological chain, so that the heavy metal pollution of water resources is harmful to ecological environment and survival development of human beings to a great extent. After the sewage with the excessive heavy metal content irrigates the land, the yield and the quality of crops can be reduced, and even plants can die; heavy metals which enter the soil cannot be decomposed or disappeared, but are easily absorbed by organisms, causing food pollution. When people ingest water and food with high heavy metal ion content, the human body cannot metabolize and degrade, and a series of diseases such as chronic poisoning, low body immunity, dysfunction, cancer and the like can be caused to a certain extent by accumulation, and even life is endangered. If copper is a trace element necessary for animals, plants and humans, trace copper can promote the growth of animals and plants, but after a certain amount of copper ions are accumulated in organisms, metabolic disorder, liver cirrhosis and liver ascites can be caused even more seriously; zinc is an important element involved in immune function, but zinc excess can inhibit activity and bactericidal activity of phagocytes, reduce immune function of human body, weaken disease resistance and thus increase susceptibility to diseases, etc. Therefore, the rapid, convenient and sensitive detection method for heavy metal ions in water has important significance in the fields of industrial and agricultural production, environmental science and the like.

Currently, in the field of detection of heavy metal ions in water, an inductively coupled plasma method, an atomic fluorescence spectrometry, an atomic absorption spectrometry and the like are widely used. However, samples for such detection methods generally require special handling and the required detection is time consuming. The fluorescent molecular sensor converts molecular identification information generated in the microscopic world into an optical signal which is easy to detect through ingenious design, and performs real-time detection on the molecular level, so that the fluorescent molecular sensor has the characteristics of high sensitivity, good selectivity, easy operation and the like, and is widely and widely applied to the detection field. Based on different optical signal conversion mechanisms, a plurality of metal ion fluorescent molecular sensors with different functions have been developed and prepared. However, most fluorescent molecular sensors present sensitive detection functions only aiming at a specific metal ion, so that the functions are single, the application limitation is large, and the increasing market demands are difficult to meet.

The julolidine group has the characteristics of high conjugated rigid coplanar structure, good optical property, strong complexing performance on metal ions and the like, and is an excellent molecular sensor construction unit [ T ].G.Jo,Y.J.Na,*J.J.Lee,M.M.Lee,S.Y.Lee,C.Kim,NewJ.Chem.,2015,39,2580]The method comprises the steps of carrying out a first treatment on the surface of the Enol tautomerism between imine groups and ortho-phenolic hydroxyl groups of Schiff base compounds can increase the sensitivity of molecular sensors, so that ultrasensitive spectral signal changes are caused after the molecular sensors react with metal ions [ J.Zhang, Z.Zhao, H.Shang, Q.Liu, F.Liu, newJ.Chem.,2019,43,14179 ]]. However, at present, cu in water is constructed by tetramethyl julolidine-phenylenediamine ²⁺ 、Zn ²⁺ Fluorescent molecular sensors with ion detection function have not been developed yet.

Disclosure of Invention

The technical purpose of the invention is to provide a method for preparing Cu ²⁺ 、Zn ²⁺ The ion has different optical detection signals, and the tetramethyl julolidine-phenylenediamine fluorescent molecule sensor is easy to prepare.

Another technical aim of the invention is to provide a method for sensitively detecting Cu in different types of water ²⁺ 、Zn ²⁺ The technical method of the ions has the advantages of sensitivity, rapidness, simplicity, easiness in operation and the like.

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

to Cu ²⁺ 、Zn ²⁺ The molecular structure of the tetramethyl julolidine-phenylenediamine fluorescent molecular sensor with ions having different optical detection signals is as follows:

to Cu ²⁺ 、Zn ²⁺ The preparation method of the tetramethyl julolidine-phenylenediamine fluorescent molecular sensor with ions having different optical detection signals is as follows:

putting alpha mmol of 1, 7-tetramethyl-8-hydroxy-9-julolidine aldehyde into a round bottom flask containing beta mL of absolute ethyl alcohol, heating to reflux, and sequentially adding delta mmol of p-phenylenediamine and gamma mu L of glacial acetic acid; continuing the reaction for 3-5 hours; filtering the mixture obtained by the reaction, washing with absolute ethyl alcohol, and drying to obtain a yellow brown tetramethyl julolidine-phenylenediamine fluorescent molecule sensor; alpha, beta, gamma and delta are 2:25:1:200.

The preparation reaction formula of the tetramethyl julolidine-phenylenediamine fluorescent molecule sensor is as follows:

the invention has the following technical effects: the tetramethyl julolidine-phenylenediamine fluorescent molecular sensor simultaneously contains three ionic action sites of rigid fatty cycloalkanamine, imine and hydroxyl, and the dual sites of imine and ortho-phenolic hydroxyl cooperate to have stronger coordination capability on metal ions, so that the sensor has Cu-ion coordination capability on Cu ²⁺ 、Zn ²⁺ The ions display significantly different optical detection signals, and the method has the advantages of high sensitivity, quick response and higher application value; the preparation process of the fluorescent molecular sensor provided by the invention has the advantages of high yield, mild synthesis conditions, simple preparation process and the like, is suitable for industrial implementation, and creates favorable conditions for popularization and application of the tetramethyl julolidine-phenylenediamine fluorescent molecular sensor.

Drawings

FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of the compound obtained in example 1-2.

FIG. 2 shows fluorescence emission performance of tetramethyl julolidine-phenylenediamine fluorescent molecular sensor after adding different metal ions into 95% DMSO distilled water solution.

FIG. 3 shows fluorescence emission performance of tetramethyl julolidine-phenylenediamine fluorescent molecular sensor after adding different metal ions into 95% DMF distilled water solution.

FIG. 4 shows that a tetramethyl julolidine-phenylenediamine fluorescent molecular sensor is simultaneously added with 10 times of Zn in 95% DMSO distilled water solution ²⁺ /Cu ²⁺ And fluorescence emission spectra of other different metal ions.

Detailed Description

The invention discloses a Cu-based alloy ²⁺ 、Zn ²⁺ The molecular structure of the tetramethyl julolidine-phenylenediamine fluorescent molecular sensor with ions having different optical detection signals is as follows:

the preparation method can be prepared by taking 1, 7-tetramethyl-8-hydroxy-9-julolidine aldehyde and p-phenylenediamine as reaction raw materials through one-step polymerization reaction, wherein the synthetic reaction formula is as follows:

example 1

Preparation of Compound A: 2mmol of 1, 7-tetramethyl-8-hydroxy-9-julolidine aldehyde is put into a round bottom flask containing 25mL of absolute ethyl alcohol, and after heating to reflux, 1mmol of p-phenylenediamine and 200 mu L of glacial acetic acid are sequentially added for continuous reaction for 3 hours; the reaction mixture was filtered, washed with absolute ethanol and dried to give a tan compound a,295.8mg, yield 47.8%.

Example 2

Preparation of compound B: 2mmol of 1, 7-tetramethyl-8-hydroxy-9-julolidine aldehyde is put into a round bottom flask containing 25mL of absolute ethyl alcohol, and after heating to reflux, 1mmol of p-phenylenediamine and 200 mu L of glacial acetic acid are sequentially added for continuous reaction for 5 hours; the reaction mixture was filtered, washed with absolute ethanol and dried to give a tan compound B,296.4mg, in 48% yield.

The compound A, B obtained in each of examples 1 and 2 was analyzed and measured, and the nuclear magnetic hydrogen spectra were identical, and the data were as follows: at the position of ¹ HNMR(CDCl ₃ 400 MHz), comprising 2 OH proton signal peaks: 13.51 (s, 2H); proton signal peaks on 2 c=n-carbons: 8.33 (s, 2H); 6 aromatic ring proton signal peaks: 7.02 (m, 4H), 6.74 (s, 2H); 16 CH ₂ Proton signal peak: 3.24 (d, 8H), 1.96 (d, 8H); 24 CH ₃ Proton signal peak, 1.33 (s, 12H), 1.26 (s, 12H), which is substantially consistent with the theory of tetramethyl julolidine-phenylenediamine fluorescent molecules. From this, it was confirmed that the molecular structure of the compound A, B was:

i.e. tetramethyl long termLony-phenylenediamine fluorescent molecules.

Example 3

Fluorescence detection performance of tetramethyl julolidine-phenylenediamine fluorescent molecular sensor on different metal ions in 95% DMSO distilled water solution: in 95% DMSO distilled water solution, the concentration is 1×10 ^-5 The tetramethyl julolidine-phenylenediamine fluorescent molecular sensor with mol/L has a maximum fluorescence emission peak at the 543nm position; 10 times equivalent of Zn is added ²⁺ After that, the maximum fluorescence emission intensity at 543nm is increased by 2.4 times; cu (Cu) ²⁺ After addition, its maximum fluorescence emission peak fluorescence emission at 543nm was almost quenched; other metal ions such as Al ³⁺ 、Fe ³⁺ 、Hg ²⁺ 、Co ²⁺ 、Mn ²⁺ 、Ni ²⁺ 、Cd ²⁺ 、Li ⁺ 、Na ⁺ 、K ⁺ 、Ba ²⁺ 、Ca ²⁺ 、Mg ²⁺ After addition, the maximum fluorescence emission of the compound molecule at the 543nm position is hardly changed obviously. These indicate that tetramethyl julolidine-phenylenediamine fluorescent molecular sensor pair Cu ²⁺ 、Zn ²⁺ Ions have significantly different fluorescent signal responses, with the potential to recognize both metal ions.

Example 4

Fluorescence detection performance of tetramethyl julolidine-phenylenediamine fluorescent molecular sensor on different metal ions in 95% DMF distilled water solution: in 95% DMF distilled water solution, the concentration is 1×10 ^-5 The molecular sensor has a maximum fluorescence emission peak at 540nm position; 10 times equivalent of Zn is added ²⁺ After that, the maximum fluorescence emission intensity at 540nm was increased by 9.5 times; cu (Cu) ²⁺ After addition, its maximum fluorescence emission peak fluorescence emission at 540nm was almost quenched; other metal ions such as Al ³⁺ 、Fe ³⁺ 、Hg ²⁺ 、Co ²⁺ 、Mn ²⁺ 、Ni ²⁺ 、Cd ²⁺ 、Li ⁺ 、Na ⁺ 、K ⁺ 、Ba ²⁺ 、Ca ²⁺ 、Mg ²⁺ After addition, the maximum fluorescence emission of the compound molecule at the 540nm position is hardly changed obviously. These indicate tetranychiumJulolidine-phenylenediamine fluorescent molecular sensor pair Cu ²⁺ 、Zn ²⁺ Ions have different fluorescent recognition potential.

Example 5

Tetramethyl julolidine-phenylenediamine fluorescent molecule sensor pair Zn ²⁺ /Cu ²⁺ Selective competition with other metal ions: at a concentration of 1X 10 ^-5 10 times equivalent of Zn is added into 95% DMSO aqueous solution of a tetramethyl julolidine-phenylenediamine fluorescent molecular sensor in mol/L ²⁺ And other metal ions such as Al ³⁺ 、Fe ³⁺ 、Hg ²⁺ 、Co ²⁺ 、Mn ²⁺ 、Ni ²⁺ 、Cd ²⁺ 、Li ⁺ 、Na ⁺ 、K ⁺ 、Ba ²⁺ 、Ca ²⁺ 、Mg ²⁺ . The fluorescence emission spectrum research of the mixed system shows that: zn with 10 times equivalent weight is added into a tetramethyl julolidine-phenylenediamine fluorescent molecule sensor ²⁺ After that, its fluorescence emission was enhanced at 543 nm; when Al is added ³⁺ 、Fe ³⁺ 、Hg ²⁺ 、Co ²⁺ 、Mn ²⁺ 、Ni ² ⁺ 、Cd ²⁺ 、Li ⁺ 、Na ⁺ 、K ⁺ 、Ba ²⁺ 、Ca ²⁺ 、Mg ²⁺ Plasma metal ion and Zn ²⁺ After the tetramethyl julolidine-phenylenediamine fluorescent molecular sensor solution is added simultaneously, the mixed system fluorescent emission spectrum and the tetramethyl julolidine-phenylenediamine fluorescent molecular sensor-Zn are mixed ²⁺ The fluorescence of the system is close. Similarly, 10 times equivalent of Cu is added simultaneously to the tetramethyl julolidine-phenylenediamine fluorescent molecule solution ² ⁺ Al and Al ³⁺ 、Fe ³⁺ 、Hg ²⁺ 、Co ²⁺ 、Mn ²⁺ 、Ni ²⁺ 、Cd ²⁺ 、Li ⁺ 、Na ⁺ 、K ⁺ 、Ba ²⁺ 、Ca ²⁺ 、Mg ²⁺ When the metal ions are generated, fluorescence of a mixed system and tetramethyl julolidine-phenylenediamine fluorescent molecular sensor-Cu ²⁺ The system fluorescence was similar. These indicate that even Zn ²⁺ 、Cu ²⁺ Tetramethyl julolidine-phenylenediamine fluorescent molecule sensor pair Zn when coexisting with other metal ions ²⁺ 、Cu ²⁺ Still watchGood selective detection performance is shown.

Example 6

Tetramethyl julolidine-phenylenediamine fluorescent molecular sensor for treating river water and Cu in tap water ²⁺ 、Zn ²⁺ Actual detection performance of ions: collecting 2 water samples of Texas area hacker river and tap water, removing suspended matters by membrane pretreatment, and determining that the water sample is free of Cu by atomic absorption spectrometry ²⁺ 、Zn ²⁺ The method comprises the steps of carrying out a first treatment on the surface of the Then adding Mg into the taken water sample ²⁺ 、Ca ²⁺ 、Li ⁺ 、Na ⁺ K is as follows ⁺ (10.00. Mu.M) into synthetic water, after which Cu was added in different amounts ²⁺ 、Zn ²⁺ The reproducibility was calculated by fluorescence test. Results are shown in the following table, for the tetramethyl julolidine-phenylenediamine fluorescent molecular sensor pair Cu ²⁺ The reproduction rate of (a) is 101-102%, and the composition is to Zn ²⁺ The reproduction rate of the method is 99% -102%, and the error is within the allowable error range; indicating that the tetramethyl julolidine-phenylenediamine fluorescent molecular sensor is used for detecting Cu in actual water sample ²⁺ 、Zn ²⁺ The analysis and detection of the method has higher accuracy and wide application prospect.

TABLE 1 actual detection Performance of tetramethyl julolidine-phenylenediamine fluorescent molecular sensor on copper and zinc ions in tap water or river water

^a n＝3； ^b Adding Mg ²⁺ 、Ca ²⁺ 、Li ⁺ 、Na ⁺ K is as follows ⁺ (10.00. Mu.M) river or tap water; test conditions 10. Mu.M of tetramethyl julolidine-phenylenediamine fluorescent molecular sensor in DMF-river/tap water (19:1) mixed solvent.

Claims

1. Detectable Cu in water ²⁺ 、Zn ²⁺ The molecular structure of the molecular sensor is as follows:

2. a detectable Cu in water as claimed in claim 1 ²⁺ 、Zn ²⁺ In detecting Cu in water ²⁺ 、Zn ²⁺ Application in ions.