阅读说明：本技术 一种含二茂铁基Schiff碱用于作为检测铈离子的荧光探针的应用 (Application of ferrocenyl Schiff base as fluorescent probe for detecting cerium ions ) 是由 刘玉婷 党阳 尹大伟 于 2020-04-30 设计创作，主要内容包括：本发明提供了一种含二茂铁基Schiff碱用于作为检测铈离子的荧光探针的应用,该含二茂铁基Schiff碱的结构为：<Image he="94" wi="195" file="DEST_PATH_IMAGE002.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>。本发明操作简单,高效,经济,绿色,环保,成本低,是一种合成二茂铁Schiff碱多离子荧光探针的高效合成方法。这类探针可实现以下的技术效果：高选择性地识别Ce<Sup>3+</Sup>离子；可以对Ce<Sup>3+</Sup>离子实现灵敏响应；可以实现对Ce<Sup>3+</Sup>离子的快速检测；以及具有较强的抗干扰能力。(The invention provides an application of a Schiff base containing ferrocenyl used as a fluorescent probe for detecting cerium ions, wherein the Schiff base containing ferrocenyl has the structure as follows: . The method is simple to operate, efficient, economic, green, environment-friendly and low in cost, and is an efficient synthesis method for synthesizing the ferrocene Schiff base multi-ion fluorescent probe. Such probes can achieve the following technical effects: highly selective recognition of Ce 3+ Ions; can be to Ce 3+ The ions realize sensitive response; can realize the reaction of Ce 3+ Fast detection of ions; and has stronger anti-interference capability.)

1. The application of the ferrocenyl Schiff base compound with the structure of formula (1) in the detection of cerium ions is as follows:

2. use according to claim 1, characterized in that it is represented by: when the sample to be tested contains Ce³⁺When the fluorescent material is ionized, the fluorescence intensity of a solution system containing the compound with the structure of the formula (1) at 323nm is obviously enhanced.

3. Use according to claim 1, characterized in that it is represented by: when the sample to be tested contains Ce³⁺When the ion is generated, the characteristic peak of the solution system containing the compound with the structure of the formula (1) at 323nm generates a red shift phenomenon.

4. As claimed inThe use according to claim 2 or 3, wherein Co is²⁺、Ni²⁺、Pb²⁺、Zn²⁺、Cr³⁺、Al³⁺、Mn²⁺、Pr^{3 +}、Dy³⁺、Tb³⁺、La³⁺、Nd³⁺And/or Ho³⁺The ions have anti-interference capability.

5. The use of claim 1, wherein the compound having the structure of formula (1) is dissolved in methanol to form a solution, which is then used to detect Ce in a sample³⁺Ions.

6. The use of claim 5, wherein the compound having the structure of formula (1) is dissolved in methanol to make 1 × 10^-5mol/L of Schiff base in methanol.

7. The use according to claim 6, wherein 0.001mol/L Ce is detectable in the sample solution to be tested³⁺Ions.

8. Use according to claim 1, when Ce in the sample to be tested is present³⁺The ion content was gradually increased in excess from the amount at which the fluorescence intensity of the system in the vicinity of 323nm was significantly increased, and the fluorescence intensity was gradually decreased.

9. The use of claim 1, wherein, in the assay, the sample to be assayed is dissolved in an appropriate amount of ultrapure water to form an aqueous solution.

10. Application of the ferrocenyl Schiff base compound with the structure of formula (1) in preparing a product for detecting cerium ions.

Technical Field

The invention relates to a method for detecting cerium ions, in particular to a fluorescent probe for detecting cerium ions and a preparation method thereof.

Background

Cerium is rich in content and has wide application in illumination, imaging, glass, catalysis and the like. Since cerium metal has a wide range of applications in various aspects of life, there have been many groups studying the effects of cerium metal on the environment, medicine and biology. Current pair of Ce³⁺The identification of (2) is mainly focused on ultraviolet, electrochemistry and atomic absorption spectrometry. Fluorescence spectroscopyThe method has the characteristics of high sensitivity, strong adaptability and small sample consumption, thereby being widely applied. However, the fluorescent probes reported at present still have some problems, including poor selectivity, poor interference resistance, and harsh synthesis conditions. In addition, probes for differential detection of cerium metal ions are still rare. Therefore, the development of selective fluorescent probes for cerium metal ions has attracted a great deal of interest in the fields of biology and environment, but there is still a challenge in obtaining simple, reliable, green, economical, and highly selective detection systems for metal ion identification.

The invention provides a fluorescent probe for detecting cerium ions, so that Ce can be effectively detected³⁺. Preparation of ferrocene Schiff base as Ce for recognition of receptor by solvent-free method³⁺The fluorescent probe is simple to operate, simple in post-treatment, economic, green, environment-friendly, efficient and low in cost, and does not need an organic solvent. For Ce of the invention³⁺The ion recognition research has great significance, and provides a novel Ce³⁺The fluorescent probe has the advantages of simple synthesis, high stability, high selectivity and good anti-interference capability.

Disclosure of Invention

The invention aims to provide a fluorescent probe for detecting cerium ions and a preparation method thereof, and the method has the advantages of simple operation, safety, high yield, low reaction cost, mild reaction conditions, greenness, simple post-treatment, high stability, high selectivity and good anti-interference capability.

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

the structural formula of a fluorescent probe for detecting cerium ions is as follows:

a method for synthesizing a fluorescent probe for detecting cerium ions comprises the following steps:

in a dry glass mortar, Amol formyl ferrocene, B mol of benzyl hydrazinodithioformate and Cmol of p-methylbenzenesulfonic acid were added and ground at room temperatureTLC monitored to completion of the reaction. After the reaction was complete, the mortar was placed in an oven at 80 ℃ for two hours and cooled to room temperature. Washing, filtering and drying to obtain a crude product. The crude product is separated and purified by silica gel column chromatography (eluent V)_(PE/EA)1:3), anhydrous Na was added₂SO₄Drying, filtering and removing the solvent by rotary evaporation to obtain the Schiff base fluorescent probe containing ferrocenyl.

The structural formula of the fluorescent probe for detecting cerium ions is as follows:

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

the invention provides a fluorescent probe for detecting cerium ions, which takes formyl ferrocene and benzyl carbazate as raw materials, takes p-toluenesulfonic acid as a catalyst, prepares ferrocene Schiff base by a solvent-free method, and takes the obtained ferrocene Schiff base as Ce³⁺The highly selective fluorescent probe of (1). The method has the advantages of simple and safe operation, high yield, low reaction cost, mild reaction conditions, greenness, simple post-treatment, high stability and selectivity for identifying ions, good anti-interference capability and the like, and has a great application prospect.

Drawings

FIG. 1 is a FT-IR spectrum of benzyl N' - (1-ferrocenyl-ethylidene) -hydrazinodithioformate of example 1.

FIG. 2 shows Schiff's base (L1-L9) in CH after 16 different metal ions are added to example 2₃The fluorescence spectrum of the OH solution shows the selectivity of different metal ions.

FIG. 3 shows that the same concentration of Ce is continuously added in example 3³⁺(0.001mol/L) after addition of Schiff base to CH₃Fluorescence spectrum in OH for identifying metal Ce³⁺In CH₃Schiff base fluorescence titration spectra in OH.

FIG. 4 is example 4Schiff base on Ce³⁺The anti-interference capability of the system. In CH₃Other metal ions (Co) present in the OH solution²⁺,Ni²⁺,Pb²⁺,Zn²⁺,Cr²⁺,Al³⁺,Mn²⁺) In the case of (3), Schiff base on Ce³⁺Selective competition is shown.

Detailed Description

The following is a further detailed description of the invention with reference to examples:

the invention takes formyl ferrocene and benzyl carbazate as raw materials, takes p-toluenesulfonic acid as a catalyst, prepares ferrocene Schiff base by a solvent-free method, and takes the obtained base as Ce³⁺A highly selective fluorescent probe recognizing a receptor. The reaction equation is as follows: