CN107043461B

CN107043461B - Preparation and application of column [5] arene and pyridine functionalized naphthaloyl derivative-based supramolecular sensor

Info

Publication number: CN107043461B
Application number: CN201710337373.1A
Authority: CN
Inventors: 林奇; 樊彦青; 郑峰; 毛鹏鹏; 关晓文; 魏太保; 张有明; 姚虹
Original assignee: Northwest Normal University
Current assignee: Northwest Normal University
Priority date: 2017-05-14
Filing date: 2017-05-14
Publication date: 2020-07-10
Anticipated expiration: 2037-05-14
Also published as: CN107043461A

Abstract

The invention designs and synthesizes a novel supramolecular sensor P5-B1 which is a column [5]]Pyridine-functionalized naphthalene bis(s) based on aromatic P5Formyl derivative B1 as a guest in H₂Performing host-guest complexation in an O-DMSO system, wherein the guest B1 penetrates into a molecular cavity of the host P5 to form a supramolecule P5-B1, and the supramolecule sensor can be complexed with Fe³⁺The coordination forms a supramolecular sensor complex P5-B1Fe, and fluorescence quenching occurs simultaneously, so that the method can be used for Fe³⁺Single selective fluorescence recognition with the lowest detection line of 5.01 × 10^‑7. Addition of F to sensor Complex P5-B1Fe^‑Green fluorescence recovery of the sensor complex, thus enabling efficient selective recognition of F^‑The lowest detection limit is 4.07 × 10^–6. And the competitive coordination identification can also be used as an 'ON-OFF-ON' type fluorescent switch, and the identification performance has important application value in the field of ion identification.

Description

Preparation and application of column [5] arene and pyridine functionalized naphthaloyl derivative-based supramolecular sensor

Technical Field

The invention relates to a column [5] arene-based supramolecular sensor, in particular to a preparation method of the supramolecular sensor, which is formed by self-assembly complexation by taking column [5] arene as a main body and a pyridine functionalized naphthaloyl derivative as an object; the invention also relates to application of the supramolecular sensor in single selective fluorescent recognition of iron ions and continuous recognition of fluorine ions, belonging to the field of ion detection.

Background

Iron (Fe), an indispensable trace element in the human body, is an important component constituting hemoglobin, myoglobin, and various enzymes, and if iron is absent in the body, it may affect the synthesis of hemoglobin and myoglobin, and may decrease the activity of some enzymes, such as cytochrome C, ribonucleotide reductase, succinate dehydrogenase, and the like. These enzymes are closely related to biological oxidation, tissue respiration, and decomposition and synthesis of neurotransmitters. Therefore, iron deficiency can cause many physiological changes, which can lead to various diseases such as low immunity, intelligence reduction, reduction of body anti-infection ability, influence on body temperature regulation ability, nerve dysfunction, reduction of working efficiency and the like, and most commonly iron deficiency anemia. The average prevalence rate of anemia of children under 7 years old in China reaches 51.6%, and the average prevalence rate of anemia of pregnant women is about 30%. Mainly caused by the increase of iron requirement of the body, insufficient dietary intake and malabsorption. In addition, bleeding from diseases such as peptic ulcer and intestinal parasites is also a significant cause of iron deficiency. Therefore, it is of great significance to detect the iron content in a living body.

The fluoride has the function of preventing dental caries, toothpaste manufacturers add fluoride to toothpaste to prevent dental caries so as to achieve the effect of preventing dental caries, toothpaste manufacturers can increase the hardness of teeth by using the fluoride-containing toothpaste, dental caries can be prevented by mainly reacting fluoride ions with substances on the surfaces of teeth and mineralizing the substances, teeth are firmed, dental caries can be reduced by using the fluoride-containing toothpaste, the fluoride can inhibit oral bacteria from producing acid and change the environment where bacteria in the oral cavity are suitable for living so as to prevent dental caries, the fluorine is used as a necessary trace element for the human body, the taking or the taking of the fluorine as too little as the trace element causes unfavorable influence on the health of the human body, the excessive fluorine intake can lead to the generation of the acid, the bacteria in the oral cavity are suitable for living environment, the dental caries can be prevented and treated, and the consumption of the fluorine as a main trace element for the human body can cause the adverse effect on the health, the excessive fluorine intake can lead to the generation of the fluorine, and the bone poisoning is caused by the excessive fluorine intake of 355 mg, the oral cavity is caused by the general bone poisoning, and the excessive fluorine is caused by the drinking of the general bone poisoning, the excessive fluorine^-) When water containing fluorine in an amount of more than 1.5 mg/L is drunk for a long period, plaque and dental diseases are liable to occur, and when the fluorine content in water is more than 4 mg/L, fluorosis may occur.Therefore, it is important for the detection of fluoride ions in the environment.

At present, various ion detection methods have been developed, and fluorescence methods have been developed as the main detection means for ion identification due to their advantages of simple operation, rapidness, high sensitivity, etc. However, in real life, various ions which are beneficial or harmful to human bodies mostly exist in the water phase, and most of the reported organic compounds which can detect the ions are hydrophobic, so that the ions are difficult to detect in the water phase; the fluorine ions have larger hydration energy, and are difficult to detect in the water phase; and the detection of iron ions and fluorine ions in the water phase by the supramolecular sensor of the host-guest complex formed by the self-assembly of the main-guest of the column aromatic hydrocarbon is reported.

Disclosure of Invention

The invention aims to provide a preparation method of a supramolecular sensor capable of singly and selectively identifying iron ions by fluorescence and continuously identifying fluorine ions;

the invention also aims to provide a specific method for the supramolecular sensor to perform single selective fluorescent recognition on iron ions and continuously recognize fluorine ions.

Preparation of mono-and supramolecular sensors

With a column [5]]Aromatic hydrocarbon as main body and pyridine functionalized naphthaloyl derivative as object in H₂In O-DMSO system (H)₂In O-DMSO system, H₂The volume ratio of the O-DMSO is 1: 8-1: 8.5. ) Self-assembly and complexation. Labeled as P5-B1. The structural formula is as follows:

the column [5] arene was synthesized according to literature procedures and labeled P5. The structural formula is as follows:

synthesis of pyridine functionalized naphthaloyl derivatives: DMF is used as a solvent, 1, 8-naphthalic anhydride and 4-aminopyridine react for 70-72 hours at 135-140 ℃ according to the molar ratio of 1: 1.2-1: 1.5, the solvent is removed by rotary evaporation, and DMF and ethanol are used for pure crystallization to obtain brown solid, namely the pyridine functionalized naphthaloyl derivative, which is marked as B1. The structural formula is as follows:

the molar ratio of the column [5] arene to the pyridine functionalized naphthaloyl derivative is 1: 1-1: 1.2.

FIG. 1 is a partial nuclear magnetic hydrogen spectrum of a supramolecular sensor, in which (a) P5 (1 × 10)^-3mol L^-1)；(b) P5(1 × 10^-3mol L^-1) And B1 (1: 1), (c) B1(1 × 10)^-3mol L^-1). The results show that the Ha, Hb, Hc, Hd proton peaks of the pyridine functionalized naphthaloyl derivative are all moved to high field, and the column [5]The H3, H4, H5, H6 proton peaks of the aromatic hydrocarbons also shift to high fields, indicating that the pyridine-functionalized naphthaloyl derivative B1 penetrates into the column [5]]Aromatic hydrocarbon cavity, so as to obtain the supramolecular sensor P5-B1.

FIG. 2 is a mass spectrum of column [5] arene assembled with B1. The results show that the column [5] arene complexes with the pyridine functionalized naphthaloyl derivative in a ratio of 1:1.

Second, supermolecule sensor fluorescence recognition Fe³⁺、F^-

1. Fluorescence properties of supramolecular sensor P5-B1

FIG. 3 shows fluorescence spectra of P5, B1, and P5-B1. As can be seen from FIG. 3, the supramolecular sensor P5-B1 has good fluorescence emission performance, and the sensor molecule P5-B1 emits green fluorescence (emission wavelength 490 nm) when the excitation wavelength is 375 nm. Whereas P5 has a weaker fluorescence, B1 has no fluorescence.

2. Selective fluorescent recognition Fe of supramolecular sensor P5-B1³⁺。

H at supramolecular sensor P5-B1₂In O-DMSO system (H)₂In O-DMSO system, H₂The volume ratio of the O-DMSO is 1: 8-1: 8.5. ) Adding 10 times of equivalent (relative to the supramolecular sensor P5-B1)Mg of (2)²⁺， Ca²⁺，Cr³⁺，Fe³⁺，Co² ⁺，Ni²⁺，Cu²⁺，Zn²⁺，Ag⁺，Cd²⁺，Hg²⁺，Pb²⁺，Ba²⁺，Al³⁺，La³⁺And Eu³⁺After mixing uniformly, only Fe is found³⁺The fluorescence of P5-B1 can be quenched (when Fe is used³⁺When added and mixed well, the fluorescence of P5-B1 is immediately quenched), thus, it is directed to Fe³⁺With selective single recognition (FIG. 4).

Meanwhile, in order to avoid the interference of other cations on the experiment, an anti-interference experiment is carried out. The results show that other cations recognize Fe for the supramolecular sensor P5-B1³⁺Without any interference (as in fig. 5). Therefore, the supramolecular sensor P5-B1 can be used for recognizing Fe³⁺The sensor of (1).

Fluorescence titration experiments show that the supramolecular sensor P5-B1 is used for Fe³⁺Has the lowest detection line of 5.01 × 10^-7。

3. Competitive coordination unity recognition F of supramolecular sensor P5-B1Fe^-Application of

H at supramolecular sensor P5-B1₂In O-DMSO system (H)₂In O-DMSO system, H₂The volume ratio of the O-DMSO is 1: 8-1: 8.5. ) 10 times equivalent (relative to the supramolecular sensor P5-B1) of Fe was added³⁺P5-B1 with Fe³⁺And (4) coordinating to obtain the supramolecular sensor P5-B1 Fe. Gradually adding different anions (Cl)^-，Br^-，I^-，F^-，Ac^-，H₂PO₄ ^-，HSO₄ ^-，SCN^-，CN^-And ClO₄ ^-) Added to P5-B1Fe, with only F^-The fluorescence of the supramolecular sensor P5-B1Fe can be turned on gradually and shows green fluorescence (as shown in fig. 6). Thus, by competitive coordination, the supramolecular sensor P5-B1Fe is able to interact with F in aqueous solution^-Has specific recognition performance.

To avoid other anionsThe interference resistance experiment is also carried out on the interference of the experiment. The results show that the addition of other anions recognizes F for the supramolecular sensor P5-B1Fe^-Without any interference (as shown in fig. 7).

By supramolecular sensor P5-B1Fe to F^-The titration experiment of (2) can calculate to obtain the pair of F of the supramolecular sensor P5-B1Fe^-Has a minimum detection limit of 4.07 × 10^–6。

4. Supramolecular sensor recognizing Fe³⁺、F^-Mechanism (2)

The supramolecular sensor P5-B1 has naphthalene ring as the group of fluorescence signal and the site of pi-pi action, the cavity is electron-rich group, and can effectively complex Fe with positive electricity³⁺Forming a P5-B1Fe supramolecular sensor; and F^-Is more electronegative than Fe³⁺Has stronger complexing ability, so that the supramolecular sensor P5-B1Fe can also recognize F with high selectivity^-。

Cation column [5]]The aromatic hydrocarbon P5 has good water solubility, contains a negative electron cavity and a certain electropositive group, and provides a pi-pi action site; the naphthalene ring in B1 is used as fluorescent signal group and pi-pi action site, and pyridine group is used as binding site. P5 and B1 at H₂The O-DMSO system can carry out host-guest complexation, and B1 penetrates into the molecular cavity of host P5 to form supramolecules P5-B1 with fluorescence change. Adding Fe³⁺Thereafter, a metal cation competing for coordination, P5-B1 and Fe, is introduced³⁺Coordinated to form another novel supramolecular sensor P5-B1Fe, due to F^-Is more electronegative than Fe³⁺Has stronger complexing ability, so that the supramolecular sensor P5-B1Fe can efficiently select and identify F^-。

In conclusion, by means of competitive coordination mechanism, the novel synthesized supramolecular sensors P5-B1 and P5-B1Fe can be designed and synthesized in H₂High-selectivity specific Fe recognition in O-DMSO mixed system³⁺And F^-. Due to F^-Has a higher enthalpy of hydration, so F is detected in water^-It is still difficult, but the synthesized supramolecular sensor P5-B1Fe can be highly selectiveIdentification F^-And the competitive coordination identification can also be used as an 'ON-OFF-ON' type fluorescent switch, and the identification performance has important application value in the field of ion identification.

Drawings

Fig. 1 is a partial nuclear magnetic hydrogen spectrum of a supramolecular sensor.

FIG. 2 shows the mass spectrum of P5 assembled with B1.

FIG. 3 shows fluorescence spectra of P5, B1, and P5-B1.

FIG. 4 is a graph showing fluorescence spectra (λ) of P5-B1 with different 10-fold equivalents of metal cations added_ex=380 nm)。

FIG. 5 shows a composition containing Fe³⁺The fluorescence spectra of the other cations were added in equal amounts to the supramolecular sensor P5-B1 solution.

FIG. 6 shows the fluorescence spectrum of supramolecular sensor P5-B1Fe with twice the equivalent of anion added.

FIG. 7 shows a graph containing F^-The fluorescence spectrum of the other anions is added into the solution of the supramolecular sensor P5-B1Fe in equal amount.

Detailed Description

The following synthesis of the supramolecular sensor P5-B1 of the invention and the univocal selective recognition of Fe by means of the specific examples³⁺、F^-The method of (1) is further illustrated.

Example 1 Synthesis of supramolecular sensor P5-B1

(1) Synthesis of host compound P5: synthesized according to the literature [ Y.Ma, X.Ji, F.Xiaong, X.Chi, C.Han, J.He, Z.Abliz, W.Chen, F.Huang, chem.Commun.47 (2011) 12340 ];

(2) synthesis of guest compound B1: transferring 15ml of DMF into a 100ml beaker, respectively adding 0.5mol of 1, 8-naphthalic anhydride and 0.55mol of 4-aminopyridine, heating to 140 ℃ for reaction for 72h, removing the solvent by rotary evaporation, and carrying out pure crystallization by using DMF and ethanol to obtain brown solid, namely the guest compound B1-the pyridine functionalized naphthaloyl derivative. Yield: 76%; M.P.220 ℃.

(3) Synthesis of supramolecular sensor P5-B1: at 5mlH₂In O-DMSO system (H)₂The volume ratio of O to DMSO is 1: 8), adding 0.5mM of the host compound P5 and 0.5mM of the guest compound B1, and self-assembly complexing (i.e. adding 0.5mM of the host compound P5 to 5ml of H first)₂And in an O-DMSO system, shaking to fully dissolve and uniformly mix the supermolecule sensor, adding 0.5mM guest compound, performing ultrasonic treatment to fully dissolve and uniformly mix the guest compound, and standing to obtain the supermolecule sensor P5-B1.

The nuclear magnetic hydrogen spectrum of the supramolecular sensor P5-B1 is shown in figure 1; the mass spectrogram is shown in FIG. 2; the fluorescence spectrum of P5-B1 is shown in FIG. 3.

Example 2 fluorescent identification of Fe³⁺

1ml (0.2 mM) of H of the supramolecular sensor molecule P5-B1 was removed₂Adding 2ml of Mg into the O-DMSO solution in a series of cuvettes respectively²⁺，Ca²⁺，Cr³⁺，Fe³⁺，Co²⁺，Ni²⁺，Cu²⁺，Zn²⁺，Ag⁺，Cd²⁺，Hg²⁺，Pb²⁺，Ba²⁺，Al³⁺，La³⁺And Eu³⁺If the fluorescence of the sensor molecule is quenched, this indicates that Fe is added (1.0 mol/L)³⁺If the fluorescence of the sensor molecule is not quenched, this indicates that the addition is not Fe³⁺。

Example 3 continuous fluorescent recognition of Fe³⁺、F^-

1ml (0.2 mM) of H of the supramolecular sensor molecule P5-B1 was removed₂Adding 2ml of Fe into a series of cuvettes in O-DMSO solution respectively³⁺An aqueous solution, the supramolecular sensor P5-B1Fe is obtained.

The obtained sensor molecule P5-B1Fe was averagely transferred to a series of cuvettes, and Cl was added to each cuvette^-，Br^-，I^-，F^-，AcO^-，H₂PO₄ ^-，HSO₄ ^-，SCN^-，CN^-And ClO₄ ^-2 × 10 (2)^-5mol/L), if the fluorescence of the sensor molecule is restored, this indicates that F is added^-If the fluorescence of the sensor molecule does not change, this indicates that F is not added^-。

Claims

1. A supramolecular sensor based on a pillared [5] arene and pyridine functionalized naphthaloyl derivative having the following structural formula:

。

2. column [5] based according to claim 1]Preparation method of supramolecular sensor of arene and pyridine functionalized naphthaloyl derivative, column [5]]Aromatic hydrocarbon as main body and pyridine functionalized naphthaloyl derivative as object in H₂Self-assembly and complexation are carried out in an O-DMSO system.

3. A process for the preparation of supramolecular sensors based on pillared [5] arene and pyridine functionalized naphthaloyl derivatives as claimed in claim 2, characterized in that: the structural formula of the main column [5] arene is as follows:

the guest pyridine functionalized naphthaloyl derivatives have the following structural formula:

the molar ratio of the column [5] arene and the guest pyridine functionalized naphthaloyl derivative of the host is 1:1.

4. Column [5] according to claim 2]The preparation method of the supramolecular sensor of the naphthaloyl derivative functionalized by aromatic hydrocarbon and pyridine is characterized in that: h₂In O-DMSO system, H₂The volume ratio of the O-DMSO is 1: 8-1: 8.5.

5. Column [5] according to claim 1]Arene and pyridine functionalized naphthaloyl derivativesSupramolecular sensor for single selective fluorescence recognition of Fe³⁺The method of (2), characterized by: h in supramolecular sensors₂Adding Mg into O-DMSO system respectively²⁺，Ca²⁺，Cr³⁺，Fe³⁺，Co²⁺，Ni²⁺，Cu²⁺，Zn²⁺，Ag⁺，Cd²⁺，Hg²⁺，Pb²⁺，Ba²⁺，Al³⁺，La³⁺And Eu³⁺If the fluorescence of the supramolecular sensor is quenched, it indicates that Fe is added³⁺(ii) a If the fluorescence of the supramolecular sensor is not quenched, it indicates that Fe is not added³⁺。

6. Column [5] according to claim 1]Supramolecular sensors of arene and pyridine functionalized naphthaloyl derivatives for the identification of F^-The method of (2), characterized by: h in supramolecular sensors₂Adding Fe into O-DMSO system³⁺Aqueous solution, supramolecular sensor and Fe³⁺Coordinating to form a supramolecular sensor complex; then respectively adding Cl into the supermolecule sensor complex^-，Br^-，I^-，F^-，AcO^-，H₂PO₄ ^-，HSO₄ ^-，SCN^-，CN^-And ClO₄ ^-If the fluorescence of the supramolecular sensor complex is restored, then it is indicated that F is added^-If the fluorescence of the supramolecular sensor complex is unchanged, it indicates that F is not added^-。