CN117430770B - Light response oxidase material based on COF, and preparation method and application thereof - Google Patents
Light response oxidase material based on COF, and preparation method and application thereof Download PDFInfo
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- CN117430770B CN117430770B CN202311765708.1A CN202311765708A CN117430770B CN 117430770 B CN117430770 B CN 117430770B CN 202311765708 A CN202311765708 A CN 202311765708A CN 117430770 B CN117430770 B CN 117430770B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 8
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 40
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- XDTZQQXBFDIDSL-UHFFFAOYSA-N 4-[3,6,8-tris(4-aminophenyl)pyren-1-yl]aniline Chemical compound C1=CC(N)=CC=C1C(C1=CC=C23)=CC(C=4C=CC(N)=CC=4)=C(C=C4)C1=C2C4=C(C=1C=CC(N)=CC=1)C=C3C1=CC=C(N)C=C1 XDTZQQXBFDIDSL-UHFFFAOYSA-N 0.000 claims abstract description 14
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/06—Amines
- C08G12/08—Amines aromatic
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
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- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
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- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
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- Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)
Abstract
The invention belongs to the technical field of high polymer material synthesis, and particularly relates to a light response oxidase material based on a COF, and a preparation method and application thereof. The invention takes 1,3,6, 8-tetra (4-aminophenyl) pyrene (TPy) and pyridine-containing aromatic dialdehydes (including 6- (4-formylphenyl) nicotinaldehyde (FPY), 2 '-bipyridine-5, 5' -dicarboxaldehyde (BPY) or 2, 5-pyridine dialdehyde (PY) and the like) as raw materials, and creates a photo-responsive oxidase material (named TPy COF) based on COF through Schiff base reaction. The TPy COF photocatalyst prepared by the invention has a narrow forbidden band, high carrier mobility and a small electron transfer barrier, is beneficial to improving the light capturing capacity, accelerating charge separation and transportation, and effectively improving the photocatalytic activity. The TPy COF prepared by the invention has obvious light response oxidase-like activity, can effectively catalyze chromogenic substrates of tetramethyl benzidine (TMB), and realizes high-sensitivity and high-selectivity detection of Glutathione (GSH), uric Acid (UA) and L-cysteine (L-Cys).
Description
Technical Field
The invention belongs to the technical field of synthesis of high polymer materials, and particularly relates to a light response oxidase-like material based on a Covalent Organic Framework (COF), and a preparation method and application thereof.
Background
The colorimetric sensor has important application value in the fields of environmental pollution, food industry, biochemical analysis, biomedicine and the like. In particular, molecular detection in the biomedical field has attracted considerable attention for its potential use in disease diagnosis and treatment. This is applicable to disease diagnosis in areas of limited resources or primary health institutions because it has no requirement for expensive instruments. Since natural enzymes such as glucose oxidase (GOx), oxidase (OXD) and Peroxidase (POD) have excellent catalytic activity, high sensitivity and substrate specificity, etc., they have been confirmed to be useful as active ingredients for designing high-efficiency biosensors for detecting various biomarkers including glucose, hydrogen peroxide, xanthine, lactic acid, L-cysteine (L-Cys), etc. Although natural enzymes have high sensitivity in colorimetric detection, there are still some limitations due to their inherent disadvantages of high cost, instability, difficulty in production and storage, etc.
The biocatalyst has the advantages of low cost, good stability, simple synthesis process, controllable nano material activity and the like, thereby having wide application prospect. Since ferrous oxide has POD-like activity, a large number of mimic enzymes having excellent catalytic activity have been developed. Because the surface structure of the nano material is difficult to control, the source of the biocatalytic site is unknown, the activity of the enzyme is low, and the catalytic mechanism is complex. Therefore, there is a need to place importance on the design of ideal biocatalysts with good catalytic activity and selectivity. Meanwhile, how to construct the biocatalyst to enable the biocatalyst to have high controllability, and further, the application of the biocatalyst in the field of colorimetric sensors is very important. Recent studies have shown that Covalent Organic Frameworks (COFs) with highly programmable structures have highly photo-responsive catalytic activity. It is expected that photoactive and nonmetallic compounds may provide an alternative, environmentally friendly, inexpensive, and prospective strategy for developing mimetic oxidases.
Disclosure of Invention
In order to solve the problems, the invention creates a light response oxidase material based on COF by taking 1,3,6, 8-tetra (4-aminophenyl) pyrene (TPy) and pyridine-containing aromatic dialdehydes (including 6- (4-formylphenyl) nicotinaldehyde (FPY), 2 '-bipyridine-5, 5' -dicarboxaldehyde (BPY) or 2, 5-pyridine dialdehyde (PY) and the like) as raw materials.
Specifically, in one aspect, the invention provides a preparation method of a light-responsive oxidase-like material based on a covalent organic framework, which comprises the steps of carrying out solvothermal reaction on 1,3,6, 8-tetra (4-aminophenyl) pyrene and pyridine-containing aromatic dialdehyde in a reaction solvent under the action of acid, collecting a reaction product, and washing and drying to obtain the light-responsive oxidase-like material based on the covalent organic framework.
As used herein, pyridine-containing aromatic dialdehydes means that at least one phenyl group in the aromatic dialdehydes contains one nitrogen heteroatom.
Further, the pyridine-containing aromatic dialdehyde is selected from 6- (4-formylphenyl) nicotinaldehyde, [2,2 '-bipyridine ] -5,5' -dicarboxaldehyde, or 2, 5-pyridinedialdehyde. Preferably, the pyridine-containing aromatic dialdehyde is selected from 6- (4-formylphenyl) nicotinaldehyde or 2, 5-pyridine dialdehyde. More preferably, the pyridine-containing aromatic dialdehyde is 6- (4-formylphenyl) nicotinaldehyde.
Further, in the preparation method of the invention, the molar ratio of the 1,3,6, 8-tetra (4-aminophenyl) pyrene to the pyridine-containing aromatic dialdehyde is 1:2.
Further, the reaction solvent is one or a mixed solvent of a plurality of 1, 4-dioxane, mesitylene, N-dimethylformamide, N-dimethylacetamide, o-dichlorobenzene, N-butanol, benzyl alcohol, methanol, ethanol, dimethyl sulfoxide, acetonitrile and cyclohexane.
Further, the reaction solvent is a mixed solvent of 1, 4-dioxane and mesitylene. Further, the volume ratio of the 1, 4-dioxane to the mesitylene in the mixed solvent is 1:1.
Further, the acid is acetic acid of 3-6 mol/L. Further, the volume ratio of the reaction solvent to the acid is 6:1. In the case that the reaction solvent is a mixed solvent of 1, 4-dioxane and mesitylene, the volume ratio of 1, 4-dioxane, mesitylene and the acid is 3:3:1.
Further, the solvothermal reaction is conducted under sealed and degassed conditions. Further, the degassing includes flash freezing with a liquid nitrogen bath, degassing through three freeze pump-thaw cycles.
Further, the solvothermal reaction includes a reaction at 120-140 ℃ for 3-7 days. Further, the solvothermal reaction includes a reaction at 120 ℃ for 5 days.
Further, the washing includes washing with acetone and tetrahydrofuran.
Further, the drying includes vacuum drying. Further, the drying includes vacuum drying at 120 ℃.
In other aspects, the invention provides a covalent organic framework-based photoresponsive oxidase-like material prepared according to the methods described herein.
Further, the covalent organic framework based photoresponsive oxidase-like material has the following structural units:or (b)Or (b)。
Preferably, the covalent organic framework based photoresponsive oxidase-like material has the following structural units:or (b)。
More preferably, the covalent organic framework based photoresponsive oxidase-like material has the following structural units:。
in other aspects, the invention provides the use of a covalent organic framework based light responsive oxidase like material as described herein for constructing a colorimetric sensor.
Further, the use is based on that the covalent organic framework based photoresponsive oxidase-like material as described herein can be used for high sensitivity and high selectivity detection of Glutathione (GSH), uric Acid (UA) and L-cysteine (L-Cys). Accordingly, the present invention provides the use of a covalent organic framework based light responsive oxidase like material as described herein for constructing a colorimetric sensor for detecting one or several of Glutathione (GSH), uric Acid (UA) and L-cysteine (L-Cys).
The beneficial effects of the invention are that
The invention takes 1,3,6, 8-tetra (4-aminophenyl) pyrene (TPy) and pyridine-containing aromatic dialdehydes (including 6- (4-formylphenyl) nicotinaldehyde (FPY), 2 '-bipyridine ] -5,5' -dicarboxaldehyde (BPY) or 2, 5-pyridine dialdehyde (PY) and the like) as raw materials to create a light response oxidase material based on COF (named as TPy COF), wherein the TPy COF corresponding to the three raw materials is named as TPy-FPY, TPy-BPY and TPy-PY respectively. The TPy COF (especially TPy-FPY) photocatalyst prepared by the invention has a narrow forbidden band, high carrier mobility and small electron transfer barrier, is beneficial to improving the light capturing capacity, accelerating charge separation and transportation, and effectively improving the photocatalytic activity. TPy COF (especially TPy-FPY) has remarkable light response oxidase-like activity and can effectively catalyze chromogenic substrates of Tetramethylbenzidine (TMB). With the advantages, the photo-activated COF photo-responsive oxidase-like activity is utilized to detect the Glutathione (GSH), uric Acid (UA) and L-cysteine (L-Cys) with high sensitivity and high selectivity, and the application prospect of the photo-activated COF photo-responsive oxidase-like activity in complex biological samples is further discussed. It is believed that such a highly efficient nano-reactor with oxide-like oxidative activity can provide some experience for the subsequent construction of colorimetric sensors, with wide application.
In comparison with the prior art, the invention uses substances used as chemical catalysis in the prior art as light response oxidase, and while COF is also useful as a light catalytic enzyme material in the prior art, no prior art indicates that COF synthesized by pyridine-containing dialdehyde is used as a light catalytic material in the invention, and the invention discloses the same and proves that the COF can be used as a colorimetric sensor; COF prepared with pyridine-free dialdehydes such as 4,4' -Biphenyldicarboxaldehyde (BPD) and terephthalaldehyde (PD) are poor in effect when used as photocatalytic oxidase materials, as shown in fig. 16b, 16c of the specification; furthermore, as shown in FIG. 13, TPy-BPD and TPy-PD are also unsuitable for use as oxidase materials because of the wide band gap. In addition, the catalyst of the prior art produces hydrogen peroxide by photocatalysis, whereas the catalyst of the present invention is capable of producing active oxygen under photocatalysis.
Drawings
FIG. 1 shows the synthetic process and chemical structure of TPy-1P.
FIG. 2 shows the synthetic process and chemical structure of TPy-2P.
FIG. 3 shows SEM images of TPy-PD at various magnifications, (a) at a magnification of 10 μm, (b) at a magnification of 5 μm, and (c) at a magnification of 2. Mu.m.
FIG. 4 shows SEM images of TPy-PY at different magnifications, (a) at a magnification of 10 μm, (b) at a magnification of 5 μm, and (c) at a magnification of 2. Mu.m.
FIG. 5 shows SEM images of TPy-BPD at various magnifications, (a) at a magnification of 10 μm, (b) at a magnification of 5 μm, and (c) at a magnification of 2. Mu.m.
FIG. 6 shows SEM images of TPy-FPY at different magnifications, (a) at 10 μm magnification, (b) at 5 μm magnification, and (c) at 2 μm magnification.
FIG. 7 shows SEM images of TPy-BPY at different magnifications, (a) at a magnification of 10 μm, (b) at a magnification of 5 μm, and (c) at a magnification of 2. Mu.m.
FIG. 8 shows a PXRD pattern presenting experimental data and simulation patterns for (a) TPy-BPD, (b) TPy-FPY, (c) TPy-BPY, (d) TPy-PD and (e) TPy-PY.
FIG. 9 shows FT-IR spectra of (a) TPy-BPD, (b) TPy-FPY, (c) TPy-BPY, (d) TPy-PD and (e) TPy-PY.
FIG. 10 shows XPS spectrum analysis of (a) TPy-BPD, TPy-FPY and TPy-BPY and (b) TPy-PD and TPy-PY.
FIG. 11 shows UV-DRS analysis of (a) TPy-2P and (b) TPy-1P.
FIG. 12 shows Mott-Schottky plots of (a) TPy-BPD, (b) TPy-FPY, (c) TPy-BPY, (d) TPy-PD and (e) TPy-PY.
FIG. 13 shows band gap distributions of (a) TPy-BPD, TPy-FPY and TPy-BPY and (b) TPy-PD and TPy-PY.
FIG. 14 shows steady state photoluminescence measurements for (a) TPy-BPD, TPy-FPY and TPy-BPY and (b) TPy-PD and TPy-PY.
FIG. 15 shows Nyquist plots of (a) TPy-BPD, TPy-FPY and TPy-BPY and (b) TPy-PD and TPy-PY and (c) TPy-BPD, TPy-FPY and TPy-BPY and (d) TPy-PD and TPy-PY.
FIG. 16 shows (a) schematic of TMB oxidation and (b) TPy-BPD, TPy-FPY and TPy-BPY and (c) TPy-PD and TPy-PY time-dependent oxidase-like activities before and after light irradiation, wherein the left half of each of the graphs of (b) and (c) is time-dependent oxidase-like activity before light irradiation and the right half is time-dependent oxidase-like activity after light irradiation.
FIG. 17 shows photo-oxidase-like activity of TPy-FPY (left panel) and TPy-PY (right panel).
FIG. 18 shows a schematic representation of absorbance at different reaction conditions.
FIG. 19 shows steady state kinetic measurements (a) and corresponding double reciprocal plots (b) using TMB as substrate under visible light irradiation for TPy-FPY (left panel) and TPy-PY (right panel) as catalysts.
FIG. 20 shows the effect of free radical scavengers on light responsive oxidase-like activity of TPy-FPY (left panel) and TPy-PY (right panel).
FIG. 21 shows the light before and after irradiation 2 - And 1 O 2 EPR spectra of signals TPy-FPY (left panel) and TPy-PY (right panel).
Fig. 22 shows a schematic diagram of the oxidation of TMB by active oxygen.
FIG. 23 shows (a) a selective colorimetric detection of glutathione according to the oxidase-like activity of TPy-FPYSchematic representation of peptides, uric acid and cysteine; (b) Ultraviolet-visible absorbance spectra of tmb+ TPy-FPY mixtures in the presence of different concentrations of glutathione; (c) Δa (Δa=a 0 -A，A 0 Is initial absorbance, a is absorbance detected after GSH addition) versus GSH concentration; (d) Uv-vis absorption spectra of tmb+ TPy-FPY mixtures in the presence of different concentrations of UA; (e) Δa (Δa=a 0 -A，A 0 Is the initial absorbance, a is the absorbance detected after UA addition) versus UA concentration; (f) Ultraviolet-visible absorption spectra of tmb+ TPy-FPY mixtures in the presence of different concentrations of Cys; (g) Δa (Δa=a 0 -a, A0 is the initial absorbance and a is the absorbance detected after addition of Cys) versus the linear calibration of Cys concentration.
Fig. 24 shows Δa (Δa=a) of TPy-PY 0 -A，A 0 Is the initial absorbance, A is the absorbance detected after addition of GSH/UA/Cys) and is a linear calibration plot of (a) GSH, (b) UA and (c) Cys concentrations.
FIG. 25 shows steady state kinetic measurements using TMB as substrate, TPy-BPY as catalyst under visible light irradiation (left panel) and the corresponding double reciprocal plot (right panel).
Fig. 26 shows Δa (Δa=a) of TPy-BPY 0 -A，A 0 Is the initial absorbance, A is the absorbance detected after addition of GSH/UA/Cys) and is a linear calibration plot of (a) GSH, (b) UA and (c) Cys concentrations.
Detailed Description
The present invention is further illustrated below with reference to specific examples, which are not intended to limit the invention in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
Example 1: synthesis of photoresponsive oxidase-like materials based on covalent organic frameworks
We used the 1,3,6, 8-tetrakis (4-aminophenyl) pyrene (TPy) building block with a series of linear dialdehydes, including phenyl (1P) and twisted biphenyl (2P) -derived building blocks, to generate imine-linked COFs in solvothermal synthesis (FIGS. 1 and 2 show schematic diagrams of the synthesis of TPy-1P COFs and TPy-2P COFs, respectively). Regarding the selection of linear dialdehyde building blocks, we selected 1, 4-Phthalaldehyde (PD), 2, 5-pyridine dialdehyde (PY), 4' -biphenyl dialdehyde (BPD), 6- (4-formylphenyl) nicotinaldehyde (FPY) and [2,2' -bipyridine ]5,5' -dicarboxaldehyde (BPY) to construct our COF to investigate the possible impact of the introduction of pyridine modules on material properties.
Specifically, the procedure for synthesizing COF using 1,3,6, 8-tetrakis (4-aminophenyl) pyrene (TPy) building blocks as raw materials with the above-described linear dialdehyde building blocks, respectively, is as follows.
TPy-PD COF synthesis. In a typical synthesis, 1,3,6, 8-tetrakis (4-aminophenyl) pyrene (85 mg,0.15 mmol), 1, 4-phthalaldehyde (32 mg,0.3 mmol), 1, 4-dioxane (1.5 mL) and mesitylene (1.5 mL) were added to a 15mL Pyrex tube. After 10 minutes of ultrasonic treatment, 0.5mL of 3M acetic acid was added. After this, the heat resistant glass tube was sealed, flash frozen with a liquid nitrogen bath, degassed by three freeze pump-thaw cycles, and then heated at 120 ℃ for 5 days. After cooling to room temperature, the precipitate was collected by filtration and washed with acetone and tetrahydrofuran. The further purified COF was dried in vacuo at 120 ℃.
TPy-PY COF synthesis. In a typical synthesis, 1,3,6, 8-tetrakis (4-aminophenyl) pyrene (85 mg,0.15 mmol), 2, 5-pyridinedialdehyde (32 mg,0.3 mmol), 1, 4-dioxane (1.5 mL) and mesitylene (1.5 mL) were added to a 15mL Pyrex tube. After 10 minutes of ultrasonic treatment, 0.5mL of 3M acetic acid was added. After this, the heat resistant glass tube was sealed, flash frozen with a liquid nitrogen bath, degassed by three freeze pump-thaw cycles, and then heated at 120 ℃ for 5 days. After cooling to room temperature, the precipitate was collected by filtration and washed with acetone and tetrahydrofuran. The further purified COF was dried in vacuo at 120 ℃.
TPy-Synthesis of BPD COF. In a typical synthesis, 1,3,6, 8-tetrakis (4-aminophenyl) pyrene (85 mg,0.15 mmol), 4' -biphenyldicarboxaldehyde (64 mg,0.3 mmol), 1, 4-dioxane (1.5 mL) and mesitylene (1.5 mL) were added to a 15mL Pyrex tube. After 10 minutes of ultrasonic treatment, 0.5mL of 3M acetic acid was added. After this, the heat resistant glass tube was sealed, flash frozen with a liquid nitrogen bath, degassed by three freeze pump-thaw cycles, and then heated at 120 ℃ for 5 days. After cooling to room temperature, the precipitate was collected by filtration and washed with acetone and tetrahydrofuran. The further purified COF was dried in vacuo at 120 ℃.
TPy-FPY COF synthesis. In a typical synthesis, 1,3,6, 8-tetrakis (4-aminophenyl) pyrene (85 mg,0.15 mmol), 6- (4-formylphenyl) nicotinaldehyde (64 mg,0.3 mmol), 1, 4-dioxane (1.5 mL) and mesitylene (1.5 mL) were added to a 15mL Pyrex tube. After 10 minutes of ultrasonic treatment, 0.5mL of 3M acetic acid was added. After this, the heat resistant glass tube was sealed, flash frozen with a liquid nitrogen bath, degassed by three freeze pump-thaw cycles, and then heated at 120 ℃ for 5 days. After cooling to room temperature, the precipitate was collected by filtration and washed with acetone and tetrahydrofuran. The further purified COF was dried in vacuo at 120 ℃.
TPy-Synthesis of BPY COF. In a typical synthesis procedure, 1,3,6, 8-tetrakis (4-aminophenyl) pyrene (85 mg,0.15 mmol), [2,2 '-bipyridine ] -5,5' -dicarboxaldehyde (64 mg,0.3 mmol), 1, 4-dioxane (1.5 mL) and mesitylene (1.5 mL) were added to a 15mL Pyrex tube. After 10 minutes of ultrasonic treatment, 0.5mL of 3M acetic acid was added. After this, the heat resistant glass tube was sealed, flash frozen with a liquid nitrogen bath, degassed by three freeze pump-thaw cycles, and then heated at 120 ℃ for 5 days. After cooling to room temperature, the precipitate was collected by filtration and washed with acetone and tetrahydrofuran. The further purified COF was dried in vacuo at 120 ℃.
Example 2: structural characterization of a covalent organic framework-based photoresponsive oxidase-like material
Scanning Electron Microscope (SEM) images of TPy-PD COF, TPy-PY COF, TPy-BPD COF, TPy-FPY COF and TPy-BPY COF are shown in FIGS. 3-7, respectively.
It was verified by powder X-ray diffraction (PXRD) patterns (FIGS. 8 a-e) that TPy-2P (i.e., TPy-BPD COF, TPy-FPY COF, and TPy-BPY COF) had two sharp diffraction peaks at 2θ≡3.2° and ≡6.4°, respectively, and TPy-1P (i.e., TPy-PD COF, TPy-PY COF) had two sharp diffraction peaks at 2θ≡3.7 ° and ≡7.5°, respectively, indicating that they had higher AA superimposed crystallinity. The same position and similar intensity of the diffraction peaks indicate that the incorporated pyridine units have little effect on the crystal structure of COF.
We collected Fourier transform infrared (FT-IR) spectra to investigate the chemical structure of TPy-2P COF and TPy-1P COF. As shown in FIG. 9, after the reaction, it includes-N-H (. Apprxeq.3344 cm) in TPy -1 ) And-c=o in 1P and 2P (≡1695 cm) -1 ) The characteristic adsorption peak of the FT-IR spectrum in the precursor of (C) drops sharply, with-c=n-bonds (+.1621 cm) -1 ) Peaks appear in the five COFs, indicating successful formation of imine bonds by the schiff base reaction.
In addition to this, XPS analysis (FIG. 10) also shows that with the introduction of pyridine blocks, the transfer of N1s binding energy is shifted to high values, as demonstrated by 2P-COF and 1P-COF (SI).
These results fully demonstrate that two different series of target compounds with identical structures, similar frameworks and different positions are successfully synthesized by Schiff base reaction.
Example 3: photophysical property characterization of photo-responsive oxidase-like materials based on covalent organic frameworks
Photophysical properties of TPy-2P and TPy-1P were systematically investigated to demonstrate their potential as simulated photoresponsive oxidases. The energy levels of the valence band maxima (VB) and conduction band minima (CB) of TPy-2P and TPy-1P were studied using Tauc and Mott-Schottky (M-S) plots. The band gaps of TPy-BPD, TPy-FPY and TPy-BPY were estimated from Tauc plot to be 2.49,2.39 and 2.31eV, respectively, and TPy-PD, TPy-pY were estimated to be 2.38 and 2.20eV, respectively (FIG. 11). This allows us to believe that the introduction of pyridine groups can effectively modulate the bandgap of TPy-COF, including TPy-2P and TPy-1P. The positive slope of the M-S plots of TPy-2P and TPy-1P indicate their n-type semiconductor behavior. By calculation, the flat band potentials of TPy-BPD, TPy-FPY and TPy-BPY were-1.29, -0.98 and-0.43V, respectively, relative to the Normal Hydrogen Electrode (NHE) (FIGS. 12 a-c). Thus, CB is estimated to be-1.49, -1.18 and-0.63V (V vs NHE). VB values calculated based on band gap and CB were 1.00, 1.21 and 1.68V for TPy-BPD, TPy-FPY and TPy-BPY, respectively. Data relating to TPy-1P are presented in FIGS. 12 d-e. For comparison, band data and O are collected in FIG. 13 2 /·O 2 - Is used for the reduction of the standard of the (a). Clearly, CB values of TPy-2P and TPy-1P are compared to O 2 /·O 2 - More negative standard reduction potential, indicating itThey have the implementation of O 2 - The capabilities of the generation. The properties of TPy-2P and TPy-1P under light excitation were studied using steady state photoluminescence spectroscopy. TPy-2P and TPy-1P show that with the introduction of pyridine blocks, the fluorescence intensity of the material decreases, meaning that electrons in the pyridine-free COF excited state tend to combine with holes and release energy in the form of photons (FIG. 14). The results indicate that the introduction of pyridine blocks can promote charge separation. In addition, photocurrent response curves and electrochemical impedance analyses were also performed on these materials. With the introduction of pyridine blocks, the material showed better electron hole generation and separation capability and carrier transport capability, indicating that the pyridine-containing COF has great potential to build up the overall photoresponsive oxidase mimetic properties (fig. 15a-b and c-d). However, we have surprisingly found that TPy-BPY has a lower photocurrent density and higher charge transfer resistance than TPy-FPY, which may result in a TPy-BPY having less final performance than TPy-FPY.
Example 4: light-driven oxidase-like activity of a light-responsive oxidase-like material based on a covalent organic framework
The excellent photocatalytic properties confer the potential of an oxidase-like enzyme. The ability of the COF to mimic the photo-oxidase was studied using TMB as a chromogenic substrate. As shown in FIGS. 16a and b-c, the small molecule substrate was oxidized by TPy-COF under light and produced the dark blue product oxTMB, where TPy-FPY and TPy-PY are the best catalytic materials in TPy-2P and TPy-1P, respectively, consistent with the photophysical property test results described above. TPy-FPY and TPy-PY were selected for further investigation in view of their excellent properties. The light-driven oxidase-like activities of TPy-FPY and TPy-PY exhibited a stepwise behavior by turning on or off light (FIG. 17). Possible influencing factors in the catalytic system were further investigated. As shown in FIG. 18, the absorbance of the system decreased with increasing pH (pH=3.5 to 7.5) and catalyst usage (10 to 40 mg/L), oxygen discharge (argon injection into the system for 0 to 10 min) and TMB content (0.015 to 0.24 mg/L). The light-driven oxidase-like activity of TPy-FPY and TPy-PY was then studied using steady state kinetics methods. As shown in FIGS. 19a and b, K of TPy-FPY m And V max 0.45mM and 0.79. Mu.M, respectively -1 While TPy-PY are respectively0.88mM and 0.73. Mu.M -1 . TPy-FPY and TPy-PY exhibit high affinity and catalytic activity for TMB compared to the reported catalytic capabilities of nanoenzymes.
Example 5: catalytic mechanism of photoresponsive oxidase-like materials based on covalent organic frameworks
In addition, the catalytic mechanisms of TPy-FPY and TPy-PY were also investigated. First, O is measured 2 The effect on this experiment was explored to explore ROS formation. As previously described, there is a positive correlation between absorbance and oxygen concentration, and the absorbance signal decreases after the solution is bubbled with argon for 10 minutes (SI). Thus, O 2 Associated with TPy-FPY or TPy-PY catalyzing TMB oxidation. Next, p-benzoquinone (p-BQ) and sodium azide (NaN) are selected 3 ) And oxalic acid ((NH) 4 ) 2 C 2 O 4 ) As superoxide anions (. O) 2 - ) Singlet oxygen 1 O 2 ) And photogeneration hole (h) + ) Is a scavenger of (a). As shown in FIG. 20, the absorption peak of oxTMB was significantly suppressed in the presence of p-BQ, and NaN was added 3 And (NH) 4 ) 2 C 2 O 4 The post absorption peak was slightly decreased. In addition, electron spin resonance (EPR) experiments were also performed to verify O 2 - And 1 O 2 . After 5 minutes of irradiation, the mixed system largely confirms O 2 - And 1 O 2 is present (fig. 21). However, no OH radicals were observed in the figure. Therefore, as shown in FIG. 22, O 2 - ， 1 O 2 And h + Is a main reaction intermediate of the oxidase mimic catalysis of TPy-FPY and TPy-PY.
Example 6: application of photoresponse oxidase-like material based on covalent organic framework in colorimetric biosensor
Because TPy-FPY has excellent oxidase-like activity, the multifunctional colorimetric biosensor based on different nano-enzyme activities is expected to be developed. Glutathione is an important intracellular antioxidant in organisms and plays an important role in physiological and pathological processes. Sensitive, selective detection of glutathione is of great importance for early diagnosis and prevention of many diseases. To this end, we have established a simple colorimetric sensing platform for detection of GSH targets. As shown in FIG. 23a, a colorimetric assay for GSH was established based on the oxidase-like activity of TPy-FPY. Under illumination conditions, TPy-FPY catalyzes the oxidation of colorless TMB to oxTMB. As a typical reducing substance, GSH is effective to reduce TMB to oxTMB, resulting in blue discoloration and a decrease in absorbance. FIG. 23b shows the absorption spectra of TMB+ TPy-FPY system in the presence of different concentrations of glutathione. In the range of 0 to 120. Mu.M, absorbance decreases in proportion to glutathione concentration. As shown in FIG. 23c, there was a good linear relationship between absorbance at 652nm and GSH concentration in the range of 0 to 60. Mu.M, correlation coefficient (R 2 ) For 0.9935, the limit of detection (LOD) was estimated to be 0.63 μm, comparable to or slightly higher than previous biocatalyst-based GSH detection colorimetry. The ultrathin TPy-FPY nano-sheet has larger surface area, can enable the TPy-FPY nano-sheet to be effectively contacted with GSH, promotes the interaction of the surfaces of the TPy-FPY nano-sheets, and improves the sensitivity of the TPy-FPY nano-sheet. The method has good sensitivity and wider detection range, and makes the TPy-FPY method an ideal method for measuring the glutathione.
UA and L-Cys exhibit similar reducibility to GSH. They may also reduce oxTMB to TMB to obtain a change in absorbance, which means that colorimetry based on TPy-FPY-like oxidase activity may be equally effective on them. Based on the above principle, we performed similar performance tests in the presence of UA and Cys. In the range of 0 to 100. Mu.M, absorbance decreased proportionally with increasing UA concentration (FIG. 23 d). As shown in FIG. 23e, there is a good linear relationship between absorbance at 652nm and GSH concentration in the range of 5 to 80. Mu.M, correlation coefficient (R 2 ) The estimated limit of detection was 0.72. Mu.M for 0.9912. On the other hand, a colorimetric sensor for determining Cys content was established based on the oxidase-like activity of TPy-FPY. With Cys concentration between 2. Mu.M and 60. Mu.M (R 2 =0.9925), the absorbance at 652nm decreases linearly. The corresponding detection limit was determined to be 0.42. Mu.M (FIGS. 23 f-g). Of course, we also tested the colorimetric detection of TPy-PY (FIG. 24), which has the best oxidase-like activity in 1P-COF. Colorimetric detection capabilities of TPy-BPY such asFig. 25 and 26. From the detection results, TPy-FPY has the strongest oxidase-like activity and a relatively wide detection range, which also shows that the catalytic activity is proportional to the detection range to a certain extent.
It should be noted that the description of the present invention and the accompanying drawings illustrate preferred embodiments of the present invention, but the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, which are not to be construed as additional limitations of the invention, but are provided for a more thorough understanding of the present invention. The above-described features are further combined with each other to form various embodiments not listed above, and are considered to be the scope of the present invention described in the specification; further, modifications and variations of the present invention may be apparent to those skilled in the art in light of the foregoing teachings, and all such modifications and variations are intended to be included within the scope of this invention as defined in the appended claims.
Claims (9)
1. A preparation method of a photoresponse oxidase-like material based on a covalent organic framework is characterized by comprising the steps of carrying out solvothermal reaction on 1,3,6, 8-tetra (4-aminophenyl) pyrene and pyridine-containing aromatic dialdehyde in a reaction solvent under the action of acid, collecting reaction products, washing and drying to obtain the photoresponse oxidase-like material based on the covalent organic framework,
wherein the pyridine-containing aromatic dialdehyde is selected from 6- (4-formylphenyl) nicotinaldehyde, [2,2 '-bipyridine ] -5,5' -dicarboxaldehyde or 2, 5-pyridinedialdehyde.
2. The method according to claim 1, wherein the molar ratio of 1,3,6, 8-tetrakis (4-aminophenyl) pyrene to pyridine-containing aromatic dialdehyde is 1:2.
3. The preparation method according to claim 1, wherein the reaction solvent is one or a mixed solvent of 1, 4-dioxane, mesitylene, N-dimethylformamide, N-dimethylacetamide, o-dichlorobenzene, N-butanol, benzyl alcohol, methanol, ethanol, dimethyl sulfoxide, acetonitrile and cyclohexane.
4. The method according to claim 3, wherein the reaction solvent is a mixed solvent of 1, 4-dioxane and mesitylene.
5. The method of claim 1, wherein the acid is 3-6mol/L acetic acid.
6. The method of claim 1, wherein the solvothermal reaction comprises reacting at 120-140 ℃ for 3-7 days.
7. A covalent organic framework based photoresponsive oxidase-like material, characterized in that it is prepared by a method according to any one of claims 1-6.
8. Use of the covalent organic framework based photoresponsive oxidase-like material of claim 7 for the construction of a colorimetric sensor.
9. The use according to claim 8, wherein the colorimetric sensor is used for detecting one or several of glutathione, uric acid and L-cysteine.
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