CN115656285A - Application of ligand-valence-variable metal charge transfer mechanism in MOF (metal-organic framework) in sensing - Google Patents
Application of ligand-valence-variable metal charge transfer mechanism in MOF (metal-organic framework) in sensing Download PDFInfo
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Abstract
The invention belongs to the technical field of application of sensors, and provides application of a ligand-valence-variable metal charge transfer mechanism in MOF (metal-organic framework) in sensing, which is applied to a PEC (proton exchange membrane) sensor of RNZ (Ribose nucleic acid), and the construction of the PEC sensor comprises the preparation of Ce-MOF, the preparation of AgNWs, the preparation of a modified electrode and the construction of RNZ-MIPES based on Ce-MOF @ AgNWs. RNZ-MIEPS from Ce-MOF @ AgNWs detects the potential applicability of RNZ in real samples.
Description
Technical Field
The invention belongs to the technical field of application of sensors, and particularly relates to application of a ligand-variable valence metal charge transfer mechanism in MOF (metal-organic framework) in sensing.
Background
Metal Organic Frameworks (MOFs) as crystalline porous coordination polymers have unique advantages of designability, high porosity, structural diversity and the like, and have attracted extensive attention in the aspects of gas separation and adsorption, catalysis, energy storage and the like. In addition, the moderate carrier recombination rate, tunable band gap, and well-defined pore size make them ideal candidates for photoactive materials. More importantly, the flexible metal ions or clusters and the variable organic ligands offer enormous possibilities for the engineering of photovoltaic electrodes. Depending on the functions implemented by MOFs, MOF-based PEC sensors can be roughly divided into two categories. One is the use of MOFs as photosensitizers to amplify light from semiconductors in PEC systemsA current signal. The other is as an optical collection and signal generation element which outputs a photocurrent signal by itself through charge separation and transmission. Porphyrins and benzene-1, 3,5-tricarboxylic acids are the most common ligands in this class of materials. These specific ligands may act as an antenna to absorb incident light and activate a second building element during irradiation to facilitate support formation. Zhang et al proposed a Protein Specific Antigen (PSA) PEC immunoassay based on DNA-mediated nanoscale zirconium-porphyrin MOFs. Antibodies were successfully immobilized on MOFs based on coordination of zirconium and phosphonate groups in DNA. Finally, dopamine is used as an electron donor, and the detection limit of the PSA sensor reaches 0.2pgmL -1 . Various porphyrin-based MOFs, including Cu-TCPP, zn-TCPP, mn-TCPP, etc., have been developed for PEC sensing by binding different recognition elements, enzymes, etc., with appropriate ligands. However, these MOFs are usually centered on a single valence metal. To our knowledge, PEC sensors based on mixed-valence metal-centered MOFs have been rarely reported. In particular, the function and charge separation kinetics of the valence-variable metal center in the photoelectric sensing process remain to be studied.
In recent years, the abuse of antibiotics has seriously affected people's daily life. Most antibiotics have cumulative toxicities and constitute a significant risk to human life and health whether ingested directly from food sources such as contaminated animal tissue or indirectly from the environment. Rozole (RNZ) is a typical nitroimidazole antibiotic with antiparasitic effects including flagellate, trichomoniasis and broad-spectrum antibacterial effects. It is worth mentioning that RNZ is very effective against trichoderma spp. Meanwhile, RNZ is an effective growth promoter, and has certain promotion effect on improving the feed conversion rate and the animal weight, so that the risk of residues in animal-derived food is increased. At present, the traditional RNZ detection method is still limited to methods such as liquid chromatography, liquid chromatography-mass spectrometry, fluorescence spectroscopy and the like, and is time-consuming and expensive. It is essential to provide a sensitive sensing analysis strategy for rapid analysis and subsequent on-site monitoring.
Disclosure of Invention
The invention aims to solve the problems recorded in the background technology and provides an application of a ligand-valence-variable metal charge transfer mechanism in MOF in sensing.
In order to achieve the purpose, the invention adopts the following technical scheme: the application of a ligand-valence-variable metal charge transfer mechanism in MOF in sensing is applied to a PEC sensor for detecting RNZ.
The PEC sensor of RNZ was constructed as follows:
step 1, preparation of Ce-MOF
30mg of NaOH are added to 10mL of a solution containing 0.025mmol of H 2 After stirring TCPP in DMF at 90 ℃ for a few minutes, a solution A was obtained, and then A was added to 10mL of 7.5mmol/L Ce (NO) 3 ) 3 -6H 2 Obtaining a solution B in the O aqueous solution, heating the solution B to 150 ℃ and refluxing for 8 hours to obtain a precipitate, centrifuging the precipitate, washing the precipitate with DMF and methanol for 3 times respectively, drying the precipitate in the air to obtain Ce-MOF powder, re-dispersing the Ce-MOF powder into the methanol solution, and preparing a 2.5mg/mL Ce-MOF solution;
step 2, preparation of AgNWs
Dissolving 0.4g polyvinylpyrrolidone in 10mL of ethylene glycol, placing the solution in 170 deg.C oil bath, stirring and heating for 1h to obtain solution C, and adding 1mL of polyvinylpyrrolidone in 5min 3 The solution was added dropwise to solution C, reacted for 5min, and 9mL of AgNO was added with a syringe 3 Continuously and slowly adding the solution into the solution C within 10min, changing the solution into a grey white emulsion after 15-20 min, pouring out a supernatant after the emulsion is kept stand for 1 day, centrifuging a bottom product, and dispersing into absolute ethyl alcohol again to prepare a 2.5mg/mL AgNWs solution;
step 3, preparing a modified electrode
Washing the ITO glass with acetone, ethanol and water in sequence, then immersing the ITO glass in a 1:1 (v/v) ethanol/NaOH (1M) solution for 15 minutes to activate the surface, washing the surface with pure water, coating 50mL of Ce-MOF solution on the surface of the ITO glass plate, continuously dripping 50 mu L of AgNWs solution on the surface of the Ce-MOF/ITO after drying, and obtaining the Ce-MOF @ AgNWs/ITO modified electrode after drying;
Using Ce-MOF @ AgNWs as a working electrode, MIP membrane was obtained by performing 40 cycles of cyclic voltammetry at a scan rate of 100mV/s in Tris-HCl buffer pH =7.0 containing 1mmol/L RNZ and 3.0mmol/L o-PD, the membrane electrode was immersed in methanol for 7 minutes to remove the template
In a preferred embodiment of the invention, step 2, agNO is added to solution C 3 The solution was prepared at intervals of 30s per 1 mL.
The principle and the beneficial effects of the invention are as follows: SEM analysis of Ce-MOF @ AgNWs showed that AgNWs bound well to the pore surfaces of Ce-MOF.
Ce-MOF @ AgNWs belong to N-type semiconductors, and their photocurrent can be enhanced by selecting an appropriate electron donor depending on the properties of the N-type semiconductor.
The electrode modified by Ce-MOF @ AgNWs also shows high-efficiency photoelectric conversion performance while maintaining good conductivity.
RNZ-MIEPS from Ce-MOF @ AgNWs detects the potential applicability of RNZ in real samples.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a graph of the RNZ-MIPES performance based on Ce-MOF @ AgNWs in the present invention;
FIG. 2 is a diagram showing that the sensor in the embodiment of the present invention has good anti-interference performance for other antibiotics and ions.
FIG. 3 Charge transfer CS Process
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the accompanying drawings are illustrative only for the purpose of explaining the present invention, and are not to be construed as limiting the present invention.
In the description of the present invention, it is to be understood that the terms "longitudinal", "lateral", "vertical", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", and the like, indicate orientations or positional relationships based on those shown in the drawings, and are used only for convenience in describing the present invention and for simplicity in description, and do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed in a particular orientation, and be operated, and thus, should not be construed as limiting the present invention.
In the description of the present invention, unless otherwise specified and limited, it is to be noted that the terms "mounted," "connected," and "connected" are to be interpreted broadly, and may be, for example, a mechanical connection or an electrical connection, a communication between two elements, a direct connection, or an indirect connection via an intermediate medium, and specific meanings of the terms may be understood by those skilled in the art according to specific situations.
The application provides an application of a ligand-valence-variable metal charge transfer mechanism in MOF in sensing, and the mechanism is applied to a PEC sensor of RNZ.
A method of constructing a PEC sensor for RNZ, comprising the steps of:
step 1, preparation of Ce-MOF
30mg of NaOH were added to 10mL of a solution containing 0.025mmol (19.8 mg) of H 2 TCPP in DMF. After stirring at 90 ℃ for several minutes, 10mL7.5Mmol/L (32.52 mg) Ce (NO) was added 3 ) 3 -6H 2 An aqueous O solution is introduced into the solution. Then, the reaction solution was heated to 150 ℃ and refluxed for 8 hours. The precipitate formed was centrifuged and washed 3 times with DMF and methanol, respectively, and then dried in air to obtain Ce-MOF powder. And then re-dispersing the powder into a methanol solution to prepare the Ce-MOF solution.
Step 2, preparation of AgNWs
Silver nanowires are prepared by a polyol process. First, 0.4g of polyvinylpyrrolidone (PVP) was dissolved in 10mL of Ethylene Glycol (EG), and then the solution was concentratedThe solution was placed in an oil bath at 170 ℃ and heated for 1h with vigorous stirring. 0.1g of AgNO 3 Dissolved in 10mL of EG and added to the PVP solution in two steps. First, 1ml of LAgNO is added within 5min 3 The solution was added dropwise to the PVP solution and after 5min of reaction, the remaining 9mL of AgNO was injected with a syringe 3 The solution was added to the reaction solution over a period of 10 min. The interval between every 1mL is about 30s. After 15-20 min, the solution turns into a gray-white emulsion. The reaction was then continued for about 30min. The resulting emulsion was allowed to stand for about one day until the silver nanowires were completely deposited on the bottom of the flask. The supernatant containing the trace amount of silver nanoparticles was decanted. And centrifuging the bottom product, and then re-dispersing the bottom product into absolute ethyl alcohol to prepare a 2.5mg/mL silver nanowire solution.
Step 3, preparation of modified electrode
Before modification, the ITO glass was washed with acetone, ethanol and water in sequence. The ITO glass was then immersed in a solution of 1:1 (v/v) ethanol/NaOH (1M) for 15 minutes to activate the surface and then rinsed clean with pure water. And (3) coating 50mL of Ce-MOF solution on the surface of the ITO glass plate, continuously dripping 50 mu L of silver nanowire solution on the surface of the Ce-MOF/ITO after drying, and drying to obtain the Ce-MOF @ AgNWs/ITO modified electrode. In addition, for comparison, ce-MOF/ITO, agNWs/ITO modified electrodes were prepared by the same method.
A MIP membrane was obtained by performing CV's for 40 cycles at a scan rate of 100mV/s in Tris-HCl buffer pH =7.0 containing 1mmol/L RNZ and 3.0mmol/L o-PD using Ce-MOF @ AgNWs as the working electrode. non-MIP (nMIP) membranes were prepared using the same protocol without RNZ. Finally, RNZ-MIPES modified electrodes were immersed in methanol for 7 minutes to remove the template.
The experimental mode is as follows
Experiment 1
The performance of the RNZ-MIPES assay based on Ce-MOF @ AgNWs was measured. When the RNZ concentration is 10 as shown in FIG. 1 - 10 mol/L-10 -5 When the mol/L range is increased, a linear equation can be obtained by converting the curve into a standard curve: Δ I =1.03444pc-0.86717 (R 2 = 0.99818), furthermore, determination of the LOD of the RNZ as repeatability is critical to ensure good and reliable results from the sensor. Therefore, 6 repeated photocurrent measurements by immersing the eluted Ce-MOF @ AgNWs MIP in an electrolyte were found to be highly stable all the time, with a relative deviation value (RSD) of only 1%, demonstrating good sensor reproducibility (FIG. 1). Secondly, the stability of the sensor is researched by re-measuring the photocurrent 24h after the sensor is placed in a refrigerator at 5 ℃, and the photocurrent attenuation of the sensor is less than 5% after 24h, so that the sensor is proved to have good stability. Finally, 5 Ce-MOF @ AgNWs MIP sensors processed by the same steps are taken to measure the photocurrents of the sensors, and the maximum relative deviation does not exceed 10 percent, thereby proving that the sensors have good reproducibility.
Experiment 2
RNZ-MIPES were examined for cross-reactivity with other common interferences, including tinidazole, diniconazole, metronidazole and other common antibiotics aureomycin, doxycycline, tetracycline, oxytetracycline, and ionic (K) with a structure similar to that of RONIAZOLE + 、Ca 2+ 、Na + 、Mg 2+ ) Further confirming the selectivity, the concentration of the interferents is 1000 times of the RNZ concentration. Fig. 2 shows that the proposed sensor exhibits good interference rejection for other antibiotics and ions, demonstrating that RNZ-MIPES has good selective discrimination for RNZ.
Experiment 3
Nitroimidazoles such as ornidazole, although they are contraindicated, are often detected in animal tissues because they have not only antibiotic action but also growth promoting action. To further investigate the applicability of the proposed sensor, animal food (i.e. milk) with added RNZ was analyzed. As listed in table 1, recovery of the known scalar-scaled RNZ ranged from 88.5% to 114.3%, with an RSD <6.4%. The results obtained also showed acceptable agreement with the results obtained by LC-MS/MS, thus indicating the potential applicability of RNZ-MIEPS based on Ce-MOF @ AgNWs to detect RNZ in real samples.
TABLE 1
In the present embodiment, the first and second electrodes are,
significant photocurrent density and on/off photocurrent ratio indicate an efficient charge transfer (CS) process. Therefore, it is necessary to elucidate the dynamics of the photon collection and CS processes of the photoelectrode. Yang et al demonstrated that in Ce-Por-MOF, when TCPP was excited, ultra-fast electron transfer occurred from the TCPP ligands to the Ce center, forming a long-lived CS state. This is an important factor in creating efficient CS processes. However, the role of the variable valence metal centers in the charge transfer process is still unclear, especially in the presence of an electron donor. Here, XPS was used to study the valence distribution of the Ce center before and after the photoelectrochemical reaction. Figure 3C shows that the splitting of the high resolution Ce3d XPS spectrum before the photoelectrochemical reaction shows nine deconvolution peaks; the peaks labeled v 0, v 'and μ' are classified as Ce (III), while the peaks labeled v, v ", v '", μ ", and μ'" are defined as characteristic peaks of Ce (IV). From the high resolution Ce3d XPS spectra, the mole percentage was semi-quantitatively estimated using equation (8), as shown below.
Wherein A is i Is the deconvolution peak area of the Ce3d XPS spectra at different binding energies. The results show that the molar percentage of Ce (IV) was 46.0% prior to PEC measurement. The Ce valence distribution after PEC measurement was also analyzed by the same procedure as shown in fig. 3D. Interestingly, the molecular percentage of Ce (IV) increased to 61.1%, indicating that the Ce center is involved in electron transfer between metal nodes of MOFs in the presence of electron donors. We have reason to speculate thatThe valence-variable metal node can provide an electronic defect state similar to that caused by doping of multiple metals, and the photoelectric conversion efficiency of the Ce-Por-MOF is greatly improved. Fig. 3B shows a reliable photocurrent generation mechanism. Under optical excitation, the TCPP ligand captures photon energy and transfers it to the Ce center, forming a long-lasting charge transfer state. The Ce-Por-MOF/AgNWs exhibit excellent optoelectronic properties in combination with the high specific surface area of the MOF and the Surface Plasmon Resonance (SPR) effect provided by AgNWs.
In the description herein, references to the description of the term "preferred embodiment," "one embodiment," "some embodiments," "an example," "a specific example" or "some examples" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
While embodiments of the present invention have been shown and described, it will be understood by those of ordinary skill in the art that: various changes, modifications, substitutions and alterations can be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents.
Claims (3)
1. Use of a ligand-valency metal charge transfer mechanism in MOF for sensing, characterized by a PEC sensor for detecting RNZ.
2. The MOF of claim 1, wherein the PEC sensor of RNZ is constructed by the following method:
step 1, preparation of Ce-MOF
30mg of NaOH are added to 10mL of a solution containing 0.025mmol of H 2 After stirring TCPP in DMF at 90 ℃ for a few minutes, a solution A is obtained, which is then added to 10mL 7.5mmol/LCe(NO 3 ) 3 -6H 2 Obtaining a solution B in the O aqueous solution, heating the solution B to 150 ℃ and refluxing for 8 hours to obtain a precipitate, centrifuging the precipitate, washing the precipitate with DMF and methanol for 3 times respectively, drying the precipitate in the air to obtain Ce-MOF powder, re-dispersing the Ce-MOF powder into the methanol solution, and preparing a 2.5mg/mL Ce-MOF solution;
step 2, preparation of AgNWs
Dissolving 0.4g polyvinylpyrrolidone in 10mL of ethylene glycol, placing the solution in 170 deg.C oil bath, stirring and heating for 1h to obtain solution C, and adding 1mL of AgNO within 5min 3 The solution was added dropwise to solution C, reacted for 5min, and 9mL of AgNO was added with a syringe 3 Continuously and slowly adding the solution into the solution C within 10min, changing the solution into a grey white emulsion after 15-20 min, pouring out a supernatant after the emulsion is kept stand for 1 day, centrifuging a bottom product, and dispersing into absolute ethyl alcohol again to prepare a 2.5mg/mL AgNWs solution;
step 3, preparing a modified electrode
Washing the ITO glass with acetone, ethanol and water in sequence, then immersing the ITO glass in a 1:1 (v/v) ethanol/NaOH (1M) solution for 15 minutes to activate the surface, washing the surface with pure water, coating 50mL of Ce-MOF solution on the surface of the ITO glass plate, continuously dripping 50 mu L of AgNWs solution on the surface of the Ce-MOF/ITO after drying, and obtaining the Ce-MOF @ AgNWs/ITO modified electrode after drying;
step 4, constructing RNZ-MIPES based on Ce-MOF @ AgNWs
The RNZ-MIPES modified electrode was immersed in methanol for 7 minutes to remove the template by performing a CV of 40 cycles at a scan rate of 100mV/s in Tris-HCl buffer PH =7.0 containing 1mmol/L RNZ and 3.0mmol/L o-PD using Ce-mof @ agnws as the working electrode to obtain a MIP membrane.
3. Use of the ligand-valency metal charge transfer mechanism in MOFs of claim 2 for sensing, wherein AgNO is added to solution C in step 2 3 The solution was applied at intervals of 30s per 1 ml.
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