阅读说明：本技术 基于柱[5]芳烃的超分子有机框架凝胶及其金属凝胶的制备和应用 (Column [5] arene-based supramolecular organic framework gel and preparation and application of metal gel thereof ) 是由 魏太保 马小强 韩增 穆天 姚虹 张有明 林奇 于 2019-10-17 设计创作，主要内容包括：本发明公开了一种基于柱[5]芳烃的超分子有机框架凝胶,是以羟基喹啉功能化的柱[5]芳烃为主体化合物,6-溴己基修饰的柱[5]芳烃为客体化合物,在正丁醇中通过原位反应形成稳定的具有蓝色聚集态诱导荧光的超分子有机框架凝胶。该超分子有机框架凝胶对Fe<Sup>3+</Sup>、Cr<Sup>3+</Sup>、Hg<Sup>2+</Sup>具有高效识别和去除作用。在柱[5]芳烃的超分子有机框架凝胶中,分别加入2倍当量的Fe<Sup>3+</Sup>、Cr<Sup>3+</Sup>,加热溶解再冷却至室温,得到稳定的金属超分子凝胶PQ-DP-Fe、PQ-DP-Cr。超分子金属凝胶PQ-DP-Fe和PQ-DP-Cr可以高选择性的超灵敏金策水溶液中的CN<Sup>-</Sup>和H<Sub>2</Sub>PO<Sub>4</Sub><Sup>-</Sup>,且该超灵敏识别过程是通过竞争配位作用实现的。(The invention discloses a column [5]]The supramolecular organic framework gel of the arene is a column [5] functionalized by hydroxyquinoline]Arene as main compound, 6-bromohexyl modified column [5]Arene is guest compound, and forms stable supermolecule organic frame gel with blue aggregation state induced fluorescence through in-situ reaction in n-butyl alcohol. The supermolecular organic framework gel is paired with Fe 3+ 、Cr 3+ 、Hg 2+ Has high-efficiency recognition andand (4) removing the effect. On the column [5]]Adding 2 times of equivalent of Fe into supramolecular organic framework gel of aromatic hydrocarbon 3+ 、Cr 3+ Heating to dissolve and cooling to room temperature to obtain stable metal supermolecular gels PQ-DP-Fe and PQ-DP-Cr. CN in ultra-sensitive gold solution with high selectivity by using supermolecular metal gel PQ-DP-Fe and PQ-DP-Cr ‑ And H 2 PO 4 ‑ And the ultrasensitive recognition process is achieved by competitive coordination.)

1. Column [5] arene-based supramolecular organic framework gels having the following structural formula:

2. the preparation method of the column [5] arene-based supramolecular organic framework gel as claimed in claim 1, wherein hydroxyquinoline functionalized column [5] arene is used as a host compound, 6-bromohexyl modified column [5] arene is used as a guest compound, the column [5] arene is heated and dissolved in n-butanol, and the host compound and the guest compound are subjected to in-situ reaction; cooling to room temperature to form stable supramolecular organic framework gel with blue aggregation state induced fluorescence;

the structural formula of the main compound, namely the hydroxyquinoline functionalized column [5] arene is as follows:

the structural formula of the guest compound 6-bromohexyl modified column [5] arene is as follows:

the molar ratio of host compound to guest compound DP was 2: 1.

3. Column [5] according to claim 2]The preparation method of the supramolecular organic framework gel of the aromatic hydrocarbon is characterized by comprising the following steps: the total amount of the body compound and guest compound in n-butanol is 1.0X 10^-4~2.0×10^-4mol/mL。

4. Column [5] according to claim 1]Detection of Fe by supramolecular organic framework gel of aromatic hydrocarbon³⁺、Hg²⁺、Cr³⁺The use of (1).

5. Column [5] according to claim 1]Supramolecular organic framework gel of aromatic hydrocarbon and detection of Fe³⁺、Hg²⁺、Cr³⁺The application of (2), which is characterized in that: adding Mg into supramolecular organic framework gel respectively²⁺，Ca²⁺，Cr³⁺，Fe³⁺, Ni²⁺，Cu²⁺，Zn^{2 +}，Ag⁺，Cd²⁺，Hg²⁺，Pb²⁺，Ba²⁺，Al³⁺，La³⁺，Co²⁺， Eu³⁺，Tb³⁺Only Fe is added to the aqueous solution of³⁺、Cr³⁺、Hg²⁺Can quench the fluorescence of the supramolecular organic framework gel.

6. Column [5] according to claim 1]Separating and removing Fe in water solution by supermolecular organic frame gel of aromatic hydrocarbon³⁺、Cr³⁺、Hg²⁺The use of (1).

7. Column [5] based according to claim 1]The preparation method of the aromatic metal supermolecule gel is that the gel is in a column [5]]Adding 2 times of equivalent of Fe into supramolecular organogel of aromatic hydrocarbon³⁺、Cr³⁺Heating to dissolve and cooling to room temperature to obtain stable metal supermolecular gels PQ-DP-Fe and PQ-DP-Cr.

8. The method of claim 7, wherein the metal supramolecular gel PQ-DP-Fe is prepared for detecting CN^-The application of (2), which is characterized in that: adding F into metal supermolecule gel PQ-DP-Fe^-、Cl^-、Br^-、I^-、AcO^-、H₂PO₄ ^-、HSO₄ ^-、N₃ ^-、SCN^-、S^2-、ClO₄ ^-、CN^-、OH^-Solution of only CN^-The addition of (a) enables the fluorescence of PQ-DP-Fe to be turned on.

9. The method of claim 7, wherein the metal supramolecular gel PQ-DP-Cr is prepared in the detection of H₂PO₄ ^-The application of (2), which is characterized in that: respectively adding F into metal supermolecular gel PQ-DP-Cr^-、Cl^-、Br^-、I^-、AcO^-、H₂PO₄ ^-、HSO₄ ^-、N₃ ^-、SCN^-、S^2-、ClO₄ ^-、CN^-、OH^-Solution of only H₂PO₄ ^-The addition of (b) enables the fluorescence of PQ-DP-Cr to be turned on.

Technical Field

The invention relates to a supermolecular organic framework gel, in particular to a gel based on a column [5]]Supramolecular organic framework gel of aromatic hydrocarbon and ultrasensitive detection of Fe by supramolecular organic framework gel³⁺、Hg²⁺、Cr³⁺The use of (a); the invention also relates to a metal gel based on the supermolecule organic framework gel and an ultrasensitive detection CN thereof^-、H₂PO₄ ^-Belonging to the field of organogel and the technical field of ion detection.

Background

Ion and molecule players play an important role in the fields of chemistry, biology, environment, etc., and are critical to the detection and separation of certain specific ions or molecules in the environment, such as: 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. Mercury (Hg) and its compounds present many health hazards, and if present in natural water, pose a threat to a wide range of people and animals. It can be accumulated in living body and transferred into human body through food chain. Accumulation of micro-organisms in the human bodyThe mercury can not be excreted by self-metabolism, and can directly cause diseases of heart, liver and thyroid gland, cause nervous system disorder, chronic mercury poisoning and even cause malignant tumor formation. Cyanide (CN)^-) Plays a considerable role in different fields, such as mining, fiber manufacturing, resin manufacturing, metallurgy and herbicide production. But CN^-Is also highly toxic and its lethal properties must be considered, its toxicity being linked to its ability to bind cytochrome C oxidase, resulting in inhibition of oxygen transport to the mitochondria, resulting in hypoxia. Therefore, a sensor with high sensitivity and high detection limit is designed for detecting CN^-Has important practical significance.

The columnar aromatic hydrocarbon is a cyclic oligomer formed by connecting hydroquinone or p-phenol ether at the para position of a benzene ring through methylene. Since 2008 Ogoshi named the macrocyclic molecule with special properties, the pillar arene is rapidly developed from the processes of initial synthesis, structure exploration, further functionalization, subject-object complexing property exploration, self-assembly research and the like, and the position of the pillar arene in the supermolecule subject-object chemistry is increasingly highlighted. The pillared arene is a novel macrocyclic main compound molecule and has various supermolecule self-assembly driving forces. Although column [5] arene-based supramolecular sensors have been reported, materials for the construction of supramolecular organic framework gels by functionalizing column [5] arenes have been less investigated.

Disclosure of Invention

The invention aims to provide column [5] arene-based supramolecular organic framework gel and a preparation method thereof;

another object of the present invention is to provide the above column [5]]Supramolecular organic framework gel of aromatic hydrocarbon to metal ion (Fe)^{3 +}、Cr³⁺And Hg²⁺) A specific method of ultra-sensitive strategy and efficient separation;

it is still another object of the present invention to provide a metal gel based on the above supramolecular organic framework gel, and the use of the metal gel in the ultrasensitive detection of CN^-、H₂PO₄ ^-The use of (1).

Preparation of mono-and supramolecular organic framework gel

The invention relates to a column [5] arene-based supramolecular organic framework gel, which is formed by taking hydroxyquinoline functionalized column [5] arene (SPQ 5) as a main compound and 6-bromohexyl-modified column [5] arene (DP) as a guest compound through in-situ reaction in n-butyl alcohol.

The structural formula of the host compound (SPQ 5) hydroxyquinoline functionalized column [5] arene is as follows:

the structural formula of the guest compound 6-bromohexyl modified column [5] arene (DP) is as follows:

the molar ratio of host compound (SPQ 5) to guest compound DP was 2: 1.

The structural formula of the supramolecular organic framework gel (PQ-DP) is as follows:

preparation of mono-and supramolecular organic framework gel (PQ-DP)

Heating and dissolving the host compound SPQ5 and the guest compound DP in n-butanol, and cooling to room temperature to obtain stable supramolecular organic framework gel labeled as PQ-DP.

The total amount of the body compound SPQ5 and the guest compound DP in n-butanol was 1.0X 10^-4~2.0×10^-4mol/mL。

FIG. 1 shows the partial NMR hydrogen spectra of SPQ5 and DP, wherein (a) is 1.04X 10^-2MSPQ5;(b) 1.04× 10^-2M SPQ5 and 2.35X 10^-2M DP;(c) 1.04 × 10^-2M SPQ5 and 4.70X 10^-2M DP;(d)1.04 × 10^-2M SPQ5 and 7.05X 10^-2And (5) M DP. FIG. 1 shows H of subject SPQ5¹，H²，H³，H⁴，H⁵，H⁶The proton peaks all move to low field, and the hydrogen proton H on the object DP^eMoving to a high field, this indicates that host SPQ5 and guest DP reacted to form a pyridinium salt in situ.

FIG. 2 is a partial concentration nuclear magnetic hydrogen spectrum of host SPQ5 and guest DP, wherein (a) is 2.07X 10^-3M；（b）4.18 × 10^-3M；（c）1.03 × 10^-2M；（d）1.66 × 10^-2M；（e）.07 × 10^-2And M. Can find that H^a，H^b，H^cAll move to high field, which indicates that pi-pi stacking exists between SPQ5 and DP, and thus can indicate that host SPQ5 and guest DP assemble into a supramolecular organic framework through host-guest interaction.

Di, supermolecule organic framework gel (PQ-DP) vs. Fe³⁺、Cr³⁺、Hg²⁺Efficient identification of

1. Fluorescent Properties of PQ-DP

FIG. 3 shows fluorescence spectra of supramolecular organic framework gel (PQ-DP). As can be seen from FIG. 3, PQ-DP has good aggregation-induced emission properties, and emits blue fluorescence (emission wavelength 465 nm) at an excitation wavelength of 335 nm.

2. Supramolecular organic framework gel (PQ-DP) vs. Fe³⁺、Cr³⁺、Hg²⁺The ultra-sensitive detection of (2):

adding 10 times of Mg into supramolecular organic framework gel (PQ-DP)²⁺，Ca²⁺，Cr³⁺，Fe³⁺, Ni²⁺，Cu²⁺，Zn²⁺，Ag⁺，Cd²⁺，Hg²⁺，Pb²⁺，Ba²⁺，Al³⁺，La³⁺，Co²⁺， Eu³⁺，Tb³⁺(0.1M) in water, it was found that only Fe was added³⁺、Cr³⁺、Hg²⁺When the fluorescence was quenched, the fluorescence of PQ-DP was quenched (see FIG. 4).

The fluorescence titration experiment shows that PQ-DP is opposite to Fe³⁺、Cr³⁺、Hg²⁺Respectively has a minimum detection limit of 1.18 × 10^-9、1.86×10^-9、9.4×10^-10M (fig. 5, 6, 7), reaching the level of ultrasensitive detection.

The infrared experiment shows that the addition of Fe into PQ-DP³⁺When the peak of PQ-DP at-C = N is 1612 cm^-1Move to 1598 cm^-1(ii) a When adding Cr³⁺The NH peak and the-C = N peak are formed by 1612 cm^-1Move to 1598 cm^-1This indicates Fe³⁺And Cr³⁺Both have a cation-pi interaction with 8-hydroxyquinoline of PQ-DP (see FIGS. 8 and 9). In Hg²⁺When Hg is added into the nuclear magnetic titration spectrogram²⁺Hydrogen proton H on quinoline ring¹，H²，H³，H⁴，H⁵，H⁶All move to a low field, indicating Hg²⁺There is a cation-pi interaction with the quinoline ring (see fig. 10).

Due to PQ-DP and Fe³⁺、Cr³⁺、Hg²⁺The corresponding complex is formed by the interaction of cation and pi, therefore, the supermolecular organic framework gel (PQ-DP) can effectively separate and remove the Fe in the water solution³⁺、Cr³⁺、Hg²⁺。

Preparation of metal supermolecule organic frame gel

1. Preparation of metal supramolecular organic framework gel (PQ-DP-M)

In supramolecular organic framework gels (PQ-DP) 1.03X 10^-5mol, n-butanol 0.10 ml), adding 2 times of equivalent of Fe respectively³⁺、Cr³⁺、Hg²⁺Then heating to dissolve and cooling to room temperature to obtain stable metal supermolecule organic frame gel PQ-DP-Fe, PQ-DP-Cr and PQ-DP-Hg, which are collectively called PQ-DP-M.

2. Metal supermolecule organic frame gel PQ-DP-Fe, PQ-DP-Cr to CN^-、H₂PO₄ ^-The ultra-sensitive detection of (2):

f is added into the prepared metal supermolecule organic frame gel PQ-DP-Fe and PQ-DP-Cr respectively^-、Cl^-、Br^-、I^-、AcO^-、H₂PO₄ ^-、HSO₄ ^-、N₃ ^-、SCN^-、S^2-、ClO₄ ^-、CN^-、OH^-Solution (0.1M) and it was found that CN was added only to PQ-DP-Fe^-When the fluorescence of PQ-DP-Fe is turned on; only adding H to PQ-DP-Cr₂PO₄ ^-When the fluorescence of PQ-DP-Cr is on. Thus, PQ-DP-Fe and PQ-DP-Cr are present separately for CN^-、H₂PO₄ ^-Has single selective fluorescence recognition function.

Fluorescence titration experiments show that the metal supermolecule organic framework gel PQ-DP-Fe is applied to CN^-The lowest detection limit is 2.12 multiplied by 10^-9(ii) a PQ-DP-Cr for HSO₄ ^-Has a minimum detection limit of 1.78 × 10^-9And M. All reached the level of ultrasensitive detection (fluorescence titration figures see fig. 5 and 7).

An infrared experiment shows that CN is added into metal supermolecule organic framework gel PQ-DP-Fe^-when-C = N peak is 1598 cm^-1Move to 1606 cm^-1And fluorescence recovery of PQ-DP-Fe, which indicates CN^-With Fe³⁺Competitive coordination occurs. When HSO is added to PQ-DP-Cr₄ ^-when-C = N peak is 1598 cm^-1Move to 1613 cm^-1In addition, simultaneous fluorescence recovery of PQ-DP-Cr also suggests HSO₄ ^-And Cr³⁺Competitive complexation occurs to reopen the fluorescence of PQ-DP-Cr (see FIG. 8 and FIG. 9 for the IR images).

In summary, columns functionalized with hydroxyquinoline [5]]Arene as main compound, 6-bromohexyl modified column [5]Aromatic hydrocarbon is a guest compound, and the host compound and the guest compound form stable supermolecule organic framework gel with blue aggregation state induced fluorescence through in-situ reaction in n-butyl alcohol. When Fe is added to PQ-DP³⁺、Cr³⁺、Hg²⁺Due to Fe³⁺、Cr³⁺、Hg²⁺Can coordinate with PQ-DP to cause fluorescence quenching of PQ-DP; when CN is added into fluorescence quenched metal supermolecule organic frame gel PQ-DP-Fe^-Due to CN^-With Fe³⁺Competition coordination leads PQ-DP fluorescence to be opened, thereby realizing Fe³⁺And CN^-Continuous reversible ultrasensitive detection; similarly, when H₂PO₄ ^-When added to PQ-DP-Cr, due to H₂PO₄ ^-With Cr in PQ-DP-Cr³⁺Coordinate to open the fluorescence, thereby realizing the aim of Cr³⁺And H₂PO₄ ^-Continuous reversible ultrasensitive detection.

Drawings

FIG. 1 is a partial nuclear magnetic titration of SPQ5 with DP.

FIG. 2 is a nuclear magnetic hydrogen spectrum of PQ-DP at partial concentration.

FIG. 3 is a fluorescent photograph of PQ-DP.

FIG. 4 fluorescence plots for detection of various analytes.

FIG. 5 is PQ-DP vs Fe³⁺And Cr³⁺Fluorescence titration map of (A) and PQ-DP-Fe vs. CN^-And PA-DP-Cr on H₂PO₄ ^-Fluorescence titration graph of (a).

FIG. 6 shows PQ-DP vs Hg²⁺Fluorescence titration graph and limit of detection graph.

FIG. 7 is PQ-DP vs Fe³⁺And Cr³⁺Detection limit diagram of (2) and PQ-DP-Fe vs. CN^-And PA-DP-Cr on H₂PO₄ ^-The detection limit map of (1).

FIG. 8 is PQ-DP vs Fe³⁺And PQ-DP-Fe on CN^-Infrared detection of (2).

FIG. 9 shows PQ-DP vs. Cr³⁺And PQ-DP-Cr on H₂PO₄ ^-Infrared detection of (2).

FIG. 10 shows PQ-DP vs. Hg²⁺Nuclear magnetic titration of (c).

Detailed Description

The synthesis and preparation of the supramolecular organic framework gel (PQ-DP) and the metal supramolecular gel (PQ-DP-M) and the application of efficient recognition and separation of multi-substrate will be further explained by the following specific examples.