阅读说明：本技术 一种卟啉基共价有机框架物及其制备方法和应用方法 (Porphyrin-based covalent organic framework material and preparation method and application method thereof ) 是由 孔泳 朱文凯 蔡文蓉 于 2021-06-18 设计创作，主要内容包括：本发明公开了一种卟啉基共价有机框架物及其制备方法和应用方法,包括：分别将四(4-苯基羧基)卟啉、苄胺、醋酸锌溶于无水乙醇中,得四(4-苯基羧基)卟啉溶液、苄胺溶液、醋酸锌溶液；将苄胺溶液逐滴加入四(4-苯基羧基)卟啉溶液中,水浴加热反应一定时间后；将醋酸锌溶液加入并搅拌反应,得卟啉基共价有机框架物,即四(4-苯基羧基)卟啉-苄胺-锌组装体。本发明能够简单、可靠、高灵敏度的检测痕量铜离子。(The invention discloses a porphyrin-based covalent organic framework material and a preparation method and an application method thereof, wherein the preparation method comprises the following steps: respectively dissolving tetra (4-phenylcarboxyl) porphyrin, benzylamine and zinc acetate in absolute ethyl alcohol to obtain a tetra (4-phenylcarboxyl) porphyrin solution, a benzylamine solution and a zinc acetate solution; dropwise adding a benzylamine solution into a tetra (4-phenylcarboxyl) porphyrin solution, and heating in a water bath for reaction for a certain time; adding zinc acetate solution, stirring and reacting to obtain a porphyrin group covalent organic framework, namely a tetra (4-phenylcarboxyl) porphyrin-benzylamine-zinc assembly. The invention can simply, reliably and highly sensitively detect the trace copper ions.)

1. A method for preparing a porphyrin-based covalent organic framework, comprising:

respectively dissolving tetra (4-phenylcarboxyl) porphyrin, benzylamine and zinc acetate in absolute ethyl alcohol to obtain a tetra (4-phenylcarboxyl) porphyrin solution, a benzylamine solution and a zinc acetate solution;

dropwise adding a benzylamine solution into a tetra (4-phenylcarboxyl) porphyrin solution, and heating in a water bath for reaction for a certain time; adding zinc acetate solution, stirring and reacting to obtain a porphyrin group covalent organic framework, namely a tetra (4-phenylcarboxyl) porphyrin-benzylamine-zinc assembly.

2. The method of preparing a porphyrin-based covalent-organic framework according to claim 1, wherein the molar ratio of tetra (4-phenylcarboxy) porphyrin to benzylamine is 1: (1-3).

3. The method for preparing a porphyrin-based covalent-organic framework according to claim 1, wherein the volume ratio of the total amount of absolute ethanol in the tetra (4-phenylcarboxy) porphyrin solution, the benzylamine solution and the zinc acetate solution to benzylamine is (7.75-34): 1.

4. the method for preparing a porphyrin-based covalent organic framework material according to claim 1, wherein the benzylamine solution is added dropwise to the tetra (4-phenylcarboxy) porphyrin solution, heated and stirred in a water bath at 40-80 ℃ and reacted for 6-12 h.

5. The method for preparing a porphyrin-based covalent organic framework according to claim 1, wherein the product tetrakis (4-phenylcarboxy) porphyrin-benzylamine-zinc assembly is obtained by adding a zinc acetate solution, heating in a water bath, stirring to react for 4-8h, cooling to room temperature, centrifuging to obtain a solid, washing with absolute ethanol for several times, and drying for 4-8 h.

6. A porphyrin-based covalent organic framework prepared by the preparation method of any one of claims 1 to 5.

7. A method for applying a porphyrin-based covalent organic framework material, wherein the porphyrin-based covalent organic framework material of claim 6 is applied to electrochemiluminescence detection of copper ions.

8. The method of using a porphyrin-based covalent-organic framework according to claim 7, comprising the steps of:

measuring the electrochemiluminescence intensity of the tetra (4-phenylcarboxyl) porphyrin-benzylamine-zinc assembly in HEPES electrolyte containing copper ions with different concentrations by using an electrochemiluminescence instrument by using a glassy carbon electrode modified by the tetra (4-phenylcarboxyl) porphyrin-benzylamine-zinc assembly as a working electrode, a saturated calomel electrode as a reference electrode, a platinum sheet electrode as a counter electrode, HEPES as electrolyte and hydrogen peroxide as a co-reaction reagent, and calculating to obtain a relation curve between the electrochemiluminescence intensity and the copper ion concentration;

and measuring the electrochemiluminescence intensity of the sample to be measured under the same condition, and obtaining the corresponding copper ion concentration through a relation curve of the electrochemiluminescence intensity and the copper ion concentration.

9. The method of using porphyrin-based covalent organic framework as described in claim 8, wherein said tetra (4-phenylcarboxy) porphyrin-benzylamine-zinc assembly modified glassy carbon electrode is prepared by a method comprising the steps of: dispersing the tetra (4-phenylcarboxyl) porphyrin-benzylamine-zinc assembly in deionized water, dripping 0.5-20 mu g of dispersion liquid with the concentration of 1-5mg/mL on the surface of a glassy carbon electrode, drying, preparing 10mM ethanol solution of tetraoctylammonium bromide, and dripping 5-15 mu L of TOAB ethanol solution on the surface of the electrode.

10. The method of using a porphyrin-based covalent-organic framework as described in claim 8, wherein said electrolyte HEPES has a pH of 4-9 and said co-reactant hydrogen peroxide is used in an amount of 0-25 mM.

Technical Field

The invention belongs to the technical field of nano material preparation and molecular recognition, and particularly relates to a porphyrin-based covalent organic framework material as well as a preparation method and an application method thereof.

Background

Cu in human body²⁺The excess or deficiency is associated with serious diseases such as gastrointestinal disorders, liver and kidney damage, Menkes disease, prion disease, Wilson disease, etc. Cu²⁺Are also considered to be heavy metals common in the environmentOne of the contaminants. Technologies based on organic fluorophores or chromophoric sensors, novel metal nanoclusters, quantum dots or nanorods, etc. have established many strategies for detecting copper ions, such as fluorescence, colorimetry, electrochemical sensors and Photoelectrochemical (PEC) sensors. However, these methods require expensive instruments and complicated operations, which limit portable detection and field application of copper ions.

Disclosure of Invention

The invention aims to overcome the defects in the prior art, and provides a porphyrin-based covalent organic framework material, a preparation method and an application method thereof, which can simply, reliably and highly sensitively detect trace copper ions.

The invention provides the following technical scheme:

a method for preparing a porphyrin-based covalent organic framework, comprising:

respectively dissolving tetra (4-phenylcarboxyl) porphyrin, benzylamine and zinc acetate in absolute ethyl alcohol to obtain a tetra (4-phenylcarboxyl) porphyrin solution, a benzylamine solution and a zinc acetate solution;

dropwise adding a benzylamine solution into a tetra (4-phenylcarboxyl) porphyrin solution, and heating in a water bath for reaction for a certain time; adding zinc acetate solution, stirring and reacting to obtain a porphyrin group covalent organic framework, namely a tetra (4-phenylcarboxyl) porphyrin-benzylamine-zinc assembly.

Further, the molar ratio of the tetra (4-phenylcarboxyl) porphyrin to the benzylamine is 1: (1-3).

Further, the volume ratio of the total amount of absolute ethyl alcohol in the tetra (4-phenylcarboxyl) porphyrin solution, the benzylamine solution and the zinc acetate solution to the benzylamine is (7.75-34): 1.

further, the benzylamine solution is added into the tetra (4-phenyl carboxyl) porphyrin solution drop by drop, and the mixture is heated and stirred in a water bath at the temperature of 40-80 ℃ to react for 6-12 h.

Further, adding a zinc acetate solution, heating in a water bath, stirring for reacting for 4-8h, cooling to room temperature, centrifuging to obtain a solid, washing the solid with absolute ethyl alcohol for several times, and drying for 4-8h to obtain a product tetra (4-phenylcarboxyl) porphyrin-benzylamine-zinc assembly.

A porphyrin-based covalent organic framework substance is prepared by a preparation method of the porphyrin-based covalent organic framework substance.

The application method of the porphyrin-based covalent organic framework is characterized in that the porphyrin-based covalent organic framework is applied to electrochemiluminescence detection of copper ions.

Further, the method comprises the following steps:

measuring the electrochemiluminescence intensity of the tetra (4-phenylcarboxyl) porphyrin-benzylamine-zinc assembly in HEPES electrolyte containing copper ions with different concentrations by using an electrochemiluminescence instrument by using a glassy carbon electrode modified by the tetra (4-phenylcarboxyl) porphyrin-benzylamine-zinc assembly as a working electrode, a saturated calomel electrode as a reference electrode, a platinum sheet electrode as a counter electrode, HEPES as electrolyte and hydrogen peroxide as a co-reaction reagent, and calculating to obtain a relation curve between the electrochemiluminescence intensity and the copper ion concentration;

and measuring the electrochemiluminescence intensity of the sample to be measured under the same condition, and obtaining the corresponding copper ion concentration through a relation curve of the electrochemiluminescence intensity and the copper ion concentration.

Further, the preparation method of the glassy carbon electrode modified by the tetra (4-phenylcarboxyl) porphyrin-benzylamine-zinc assembly comprises the following steps: dispersing the tetra (4-phenylcarboxyl) porphyrin-benzylamine-zinc assembly in deionized water, dripping 0.5-20 mu g (preferably 5 mu g) of dispersion liquid with the concentration of 1-5mg/mL on the surface of a glassy carbon electrode, drying, preparing 10mM ethanol solution of tetraoctylammonium bromide, and dripping 5-15 mu L of TOAB ethanol solution on the surface of the electrode.

Further, the pH of the electrolyte HEPES is 4-9, preferably 5, and the co-reactant hydrogen peroxide is used in an amount of 0-25mM, preferably 15 mM.

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

(1) the preparation method of the porphyrin-based covalent organic framework provided by the invention is simple and feasible, and the prepared tetra (4-phenylcarboxyl) porphyrin-benzylamine-zinc assembly has better electrochemiluminescence performance and electron transmission capability;

(2) the application method of the porphyrin-based covalent organic framework provided by the invention uses the glassy carbon electrode modified by the tetra (4-phenylcarboxyl) porphyrin-benzylamine-zinc assembly as a working electrode, can realize the detection of trace copper ions, has the detection limit as low as 1.3068nmol/L, and has the advantages of high sensitivity, reliable result and simple operation method.

Drawings

FIG. 1 is a graph of ECL strength of TCPP-BZA-Zn assemblies of examples 1-3, A, B, C corresponding to examples 1, 2 and 3, respectively;

FIG. 2 is a scanning electron micrograph of TCPP according to example 2;

FIG. 3 is a scanning electron micrograph of the TCPP-BZA-Zn assembly prepared in example 2;

FIG. 4 is an infrared spectrum of TCPP, TCPP-BZA and TCPP-BZA-Zn assemblies in example 2;

FIG. 5 is a cyclic voltammogram of TCPP, BZA and TCPP-BZA-Zn assemblies of example 2;

FIG. 6 is a graph of ECL strength comparisons of TCPP, the TCPP-BZA-Zn assembly of example 2, and the TCPP-BZA assembly of the comparative example;

FIG. 7 is a log plot of ECL intensity versus copper ion concentration for example 2.

Detailed Description

The invention is further described below with reference to the accompanying drawings. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.

Example 1

Dissolving 2.4mg of tetra (4-phenylcarboxyl) porphyrin (TCPP, molecular weight 790.77) in 3mL of absolute ethyl alcohol, dispersing 0.5mL of Benzylamine (BZA) in 2.5mL of absolute ethyl alcohol, dropwise adding the benzylamine solution into the tetra (4-phenylcarboxyl) porphyrin solution, and heating in a water bath at 65 ℃ and stirring for 8 hours; dissolving 0.65mg of zinc acetate (molecular weight of 219.51) in 1mL of absolute ethyl alcohol, dropwise adding the obtained solution into the reaction solution, continuously stirring for 6h, cooling to room temperature, centrifuging the solid, washing with absolute ethyl alcohol for three times, and drying for 6h to obtain the tetra (4-phenylcarboxy) porphyrin-benzylamine-zinc assembly (TCPP-BZA-Zn assembly).

Dispersing 1mg of TCPP-BZA-Zn assembly in 1mL of ultrapure water to obtain a dispersion liquid, transferring 5 mu L of the dispersion liquid by using a liquid transfer gun, dripping and coating the dispersion liquid on the surface of a Glassy Carbon Electrode (GCE), airing at room temperature, dripping 10 mu L of ethanol solution of tetraoctylammonium bromide (TOAB) with the concentration of 10mM on the surface of the electrode, and airing to prepare the glassy carbon electrode (TCPP-BZA-Zn/GCE) modified by the tetra (4-phenylcarboxyl) porphyrin-benzylamine-zinc assembly. TCPP-BZA-Zn/GCE is used as a working electrode, a saturated calomel electrode is used as a reference electrode, a platinum sheet electrode is used as a counter electrode, HEPES with pH of 5 is used as electrolyte, 15mM hydrogen peroxide is used as a co-reaction reagent, and an Electrochemiluminescence (ECL) intensity test is carried out on the TCPP-BZA-Zn assembly through an electrochemiluminescence instrument.

Example 2

Dissolving 2.4mg of tetra (4-phenylcarboxyl) porphyrin in 3mL of absolute ethyl alcohol, dispersing 0.5mL of benzylamine in 2.5mL of absolute ethyl alcohol, dropwise adding the benzylamine solution into the tetra (4-phenylcarboxyl) porphyrin solution, and heating and stirring in a water bath for 8 hours at the temperature of 65 ℃; dissolving 1.3mg of zinc acetate in 1mL of absolute ethyl alcohol, dropwise adding the mixture into the reaction solution, continuously stirring for 6h, cooling to room temperature, washing the centrifuged solid with absolute ethyl alcohol for three times, and drying for 6h to obtain the TCPP-BZA-Zn assembly.

And dispersing 1mg of TCPP-BZA-Zn assembly in 1mL of ultrapure water to obtain a dispersion liquid, transferring 5 mu L of the dispersion liquid by using a liquid transfer gun, dripping and coating the dispersion liquid on the surface of a glassy carbon electrode, airing at room temperature, dripping and coating 10 mu L of a TOAB ethanol solution with the concentration of 10mM on the surface of the electrode, and airing to prepare the TCPP-BZA-Zn/GCE. TCPP-BZA-Zn/GCE is used as a working electrode, a saturated calomel electrode is used as a reference electrode, a platinum sheet electrode is used as a counter electrode, HEPES with pH of 5 is used as electrolyte, 15mM hydrogen peroxide is used as a co-reaction reagent, and an Electrochemiluminescence (ECL) intensity test is carried out on the TCPP-BZA-Zn assembly through an electrochemiluminescence instrument.

Measuring the electrochemiluminescence intensity of the TCPP-BZA-Zn assembly in HEPES electrolyte containing copper ions with different concentrations by an electrochemiluminescence instrument, and calculating to obtain a relation curve between the electrochemiluminescence intensity and the copper ion concentration.

TCPP-BZA-Zn/GCE is used as a working electrode, a saturated calomel electrode is used as a reference electrode, a platinum sheet electrode is used as a counter electrode, HEPES is used as electrolyte, a cyclic voltammetry test is carried out by an electrochemical workstation, and the voltage range of the cyclic voltammetry test is-1.5-0V so as to probe the electrochemical activity of the material.

Example 3

Dissolving 2.4mg of tetra (4-phenylcarboxyl) porphyrin in 3mL of absolute ethyl alcohol, dispersing 0.5mL of benzylamine in 2.5mL of absolute ethyl alcohol, dropwise adding the benzylamine solution into the tetra (4-phenylcarboxyl) porphyrin solution, and heating and stirring in a water bath for 8 hours at the temperature of 65 ℃; dissolving 1.95mg of zinc acetate (molecular weight of 219.51) in 1mL of absolute ethyl alcohol, dropwise adding the mixture into the reaction solution, continuously stirring for 6h, cooling to room temperature, washing the centrifuged solid with absolute ethyl alcohol for three times, and drying for 6h to obtain the TCPP-BZA-Zn assembly.

Dispersing 1mg of TCPP-BZA-Zn assembly in 1mL of ultrapure water to obtain a dispersion, transferring 5 mu L of the dispersion by using a liquid transfer gun, dripping the dispersion on the surface of a Glassy Carbon Electrode (GCE), airing at room temperature, dripping 10 mu L of a TOAB ethanol solution with the concentration of 10mM on the surface of the electrode, and airing to prepare the TCPP-BZA-Zn/GCE. TCPP-BZA-Zn/GCE is used as a working electrode, a saturated calomel electrode is used as a reference electrode, a platinum sheet electrode is used as a counter electrode, HEPES with pH of 5 is used as electrolyte, 15mM hydrogen peroxide is used as a co-reaction reagent, and an Electrochemiluminescence (ECL) intensity test is carried out on the TCPP-BZA-Zn assembly through an electrochemiluminescence instrument.

Comparative example

Dissolving 2.4mg of tetra (4-phenylcarboxyl) porphyrin in 3mL of absolute ethyl alcohol, dispersing 0.5mL of benzylamine in 2.5mL of absolute ethyl alcohol, dropwise adding the benzylamine solution into the tetra (4-phenylcarboxyl) porphyrin solution, and heating and stirring in a water bath for 8 hours at the temperature of 65 ℃; adding 1mL of absolute ethyl alcohol, dropwise adding the absolute ethyl alcohol into the reaction solution, continuously stirring for 6h, cooling to room temperature, washing the centrifuged solid with absolute ethyl alcohol for three times, and drying for 6h to obtain the TCPP-BZA assembly.

And (2) dispersing 1mg of the TCPP-BZA-Zn assembly in 1mL of ultrapure water to obtain a dispersion liquid, transferring 5 mu L of the dispersion liquid by using a liquid transfer gun, dripping and coating the dispersion liquid on the surface of a Glassy Carbon Electrode (GCE), airing at room temperature, dripping 10 mu L of a TOAB ethanol solution with the concentration of 10mM on the surface of the electrode, and airing to prepare the TCPP-BZA composite material modified glassy carbon electrode. The TCPP-BZA composite material modified glassy carbon electrode is used as a working electrode, a saturated calomel electrode is used as a reference electrode, a platinum sheet electrode is used as a counter electrode, HEPES with pH of 5 is used as electrolyte, 15mM hydrogen peroxide is used as a co-reaction reagent, and an Electrochemiluminescence (ECL) intensity test is carried out on the TCPP-BZA-Zn assembly through an electrochemiluminescence instrument.

Analysis of Experimental data

As shown in FIG. 1, in examples 1 to 3, the molar ratios of tetra (4-phenylcarboxy) porphyrin to zinc acetate were 1:1, 1:2, and 1:3, respectively, and the ECL strengths of the three were all high, with the ECL strength of example 2 being the highest and the stability being good.

As shown in FIG. 2, the TCPP monomer in example 2 exhibits a random blocky structure.

As shown in FIG. 3, the TCPP-BZA-Zn assembly of example 2 has a rod-like structure with a small size.

As shown in FIG. 4, the successful introduction of benzylamine can be seen from the IR spectra of TCPP, TCPP-BZA and TCPP-BZA-Zn assemblies in example 2.

As shown in fig. 5, the cyclic voltammograms of TCPP, BZA, and TCPP-BZA-Zn in example 2 show that BZA has better electrochemical activity, and the electrochemical activity of the prepared TCPP-BZA-Zn is significantly enhanced compared with the original TCPP.

As shown in FIG. 6, comparing the ECL performance of TCPP, the TCPP-BZA-Zn assembly of example 2 and the TCPP-BZA assembly of the comparative example, it can be seen that the ECL strength of the TCPP-BZA-Zn assembly is significantly higher than that of the TCPP and TCPP-BZA assemblies.

As shown in FIG. 7, the electrochemiluminescence intensity in HEPES electrolyte solution containing copper ions of different concentrations was measured by an electrochemiluminescence apparatus, and the electrochemiluminescence intensity was plotted in a logarithmic curve with respect to the concentration of copper ions, R²= 0.98548. And measuring the electrochemiluminescence intensity of the sample to be measured under the same condition by taking the curve as a standard curve, and calculating to obtain the corresponding copper ion concentration through the curve.

In summary, the preparation method of the porphyrin-based covalent organic framework provided by the invention is simple and feasible, and the prepared tetra (4-phenylcarboxyl) porphyrin-benzylamine-zinc assembly has better electrochemiluminescence performance and electron transmission capability; the application method of the porphyrin-based covalent organic framework provided by the invention uses the glassy carbon electrode modified by the tetra (4-phenylcarboxyl) porphyrin-benzylamine-zinc assembly as a working electrode, can realize the detection of trace copper ions, has the detection limit as low as 1.3068nmol/L, and has the advantages of high sensitivity, reliable result and simple operation method.

The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.