CN114106815A - Preparation method of rare earth MOFs protein fiber composite fluorescent sensing material - Google Patents
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Abstract
The invention belongs to the technical field of fluorescent sensing material application, and particularly relates to a preparation method of a rare earth MOFs protein fiber composite fluorescent sensing material. The invention provides a preparation method of a rare earth MOFs protein fiber composite fluorescent sensing material, which utilizes a large number of active groups, such as carboxyl, hydroxyl, amino and the like, on the surface of a protein fiber to provide sites for reacting with an Ln-MOFs material. And simultaneously, pre-modifying the fiber substrate, and carrying out Atomic Layer Deposition (ALD) technical treatment on the fiber substrate assisted by a small-molecule polycarboxylic acid bridging ligand or the surface to regulate and control the binding force between the fiber substrate and Ln-MOFs and the morphology and the loading capacity of the nanocrystalline. The prepared Ln-MOFs/protein fiber functional composite crystalline material effectively realizes double regulation and control of structure and function, thereby realizing the application in the field of fluorescent sensing of pH value, temperature and micromolecules in human physiological environment.
Description
Technical Field
The invention belongs to the technical field of fluorescent sensing material application, and particularly relates to a preparation method of a rare earth MOFs protein fiber composite fluorescent sensing material.
Background
Human health is closely related to factors such as pH, temperature, small molecules in physiological environments, for example, abnormal pH in tissues may reflect related diseases; the infection process of the virus is often accompanied by the temperature change of the whole or part of the organism; in vivo small molecule secretion disorder such as dopamine can cause neurological related diseases such as Parkinson. How to rapidly and accurately detect one or more factors and realize early prevention and treatment is very important for human health. The detection methods reported in the previous literature mainly include electrochemical detection, high performance liquid chromatography, fluorescence spectroscopy and the like. The electrochemical detection is quick, simple and convenient, the operation is convenient, but the reproducibility of the test result is not good. The high performance liquid chromatography has high accuracy, but has high cost, long time consumption and larger detection error of pH value and temperature. The fluorescence spectroscopy has the advantages of fast response, high sensitivity, low cost, non-contact and the like, is widely applied, but firstly needs to prepare a fluorescence sensing material with excellent performance.
The rare earth metal organic framework materials (Ln-MOFs) are three-dimensional network crystalline materials with high crystallization, which are formed by taking rare earth metals and metal clusters as nodes and self-assembling the rare earth metals and the metal clusters with organic ligands through coordination bonds, hydrogen bonds or intermolecular forces, have excellent fluorescence performance, high sensitivity, fast response and good selectivity, and arouse great research interest of people. For example, the preparation method and application of a lanthanide metal and tetraphenylethylene group-based MOFs material disclosed by the national intellectual property office { patent number: CN201911338441.1, which takes tetraphenylethylene as a construction main body, selects lanthanide metals with various coordination modes and high coordination numbers as construction nodes, and self-assembles by a hydrothermal synthesis method to obtain lanthanide-tetraphenylethylene porous MOFs materials; the rigid framework and the pore channels can be in a seriesSelective recognition of Fe in metal cations3Using fluorescence emission as a corresponding signal to realize a visual identification and detection process through good fluorescence emission performance of the tetraphenylethylene ligand; and further designing the identification process as ion detection test paper which is more convenient and rapid for Fe3+ detection provides a convenient condition; compared with the prior art, the compound synthesized by the invention is a first lanthanide-tetraphenyl vinyl-based porous MOFs material, and is used in the identification application of metal cations through performance evaluation, and the ion identification and detection of the compound in water or other solution systems have good application prospects.
However, most of the currently reported Ln-MOFs materials are bulk crystals, and are difficult to machine and form, so that the application prospect of the Ln-MOFs materials in the aspect of human body sensor assembly is greatly limited. Therefore, how to make Ln-MOFs have an easy-to-use form and apply the Ln-MOFs to the rapid detection in the field of pH value, temperature and micromolecule fluorescence sensing in the human physiological environment is a difficult point which needs to be overcome by the application of the Ln-MOFs at present.
Disclosure of Invention
Aiming at the technical problems existing in the application of the existing rare earth metal organic framework material in the field of fluorescence sensing of pH value, temperature and micromolecules in the physiological environment of a human body, the invention provides the preparation method of the rare earth MOFs protein fiber composite fluorescence sensing material which is reasonable in formula, simple in method and capable of effectively realizing the application of the rare earth metal organic framework material in the field of fluorescence sensing of the human body.
In order to achieve the purpose, the invention adopts the technical scheme that the preparation method of the rare earth MOFs protein fiber composite fluorescent sensing material comprises the following effective steps:
a. fully dissolving nitrate and micromolecular organic ligand of rare earth ions or mixed ions of the rare earth ions and the rare earth ions or the rare earth ions and transition metal ions in H2O;
b. adding the mixture obtained in the step a into a hydrothermal reaction kettle, placing a protein fiber substrate material in the hydrothermal reaction kettle, and adjusting the pH value to be neutral or weakly alkaline;
c. and (3) putting the adjusted material into a temperature-controlled oven, heating the material from room temperature, controlling the temperature, and cooling the material to room temperature after the temperature control is finished, so that MOFs of rare earth ions or mixed ions of the rare earth ions and metal ions are fully crystallized, and the MOFs is self-assembled on the surface of the protein fiber substrate material layer by layer to prepare the rare earth MOFs protein fiber composite material of the rare earth ions or the mixed ions of the rare earth ions and transition metal ions.
Preferably, the method further comprises the following steps:
c1, pretreating the protein fiber substrate material, and using 0.5% NaHCO3Repeatedly cooking the solution twice, then cooking once by using a deionized water solution, then taking out, repeatedly washing by using deionized water, and airing at room temperature to obtain the degummed protein fiber substrate material;
c2, and then depositing a nano-layer thick TiO layer on the obtained protein fiber substrate material by using an atomic layer deposition technology2Or Al2O3A thin film is formed, and the protein fiber substrate material modified by the atomic layer deposition technology is obtained;
preferably, in the step c, the protein fiber substrate material is one of silk fibroin, wool protein, cashmere protein, down feather protein, corn protein or soybean protein short fiber and fabric thereof.
Preferably, in step a, the rare earth ion is Eu3+、Tb3+、Dy3+、Sm3+、La3+The rare earth ion in the mixed ion of rare earth ion and rare earth ion or rare earth ion and transition metal ion is Eu3+、Tb3+、Dy3+、Sm3+、La3+The transition metal ion is Cu2+、Zn2+、Fe3+、Mg2+、Al3+。
Preferably, in the step a, the small molecule organic ligand is a carboxylic acid, imidazole or heterocyclic small molecule ligand.
Preferably, in the step a, nitrate and small component of rare earth ions or mixed ions of the rare earth ions and the rare earth ions or the rare earth ions and transition metal ions are addedThe organic ligand and the protein macromolecular ligand are fully dissolved in H2And (4) in O.
Preferably, the protein macromolecular ligand is one of plant protein macromolecules such as soybean, corn, peanut and the like or animal protein macromolecules such as silk, hairiness and the like.
Preferably, the molar ratio of the rare earth ions or the mixed ions of the rare earth ions and the rare earth ions or the rare earth ions and the transition metal ions to the small-molecule organic ligands is 1: 1 to 6.
Preferably, the molar ratio of the rare earth ions to the rare earth ions or the rare earth ions to the transition ions in the mixed metal ions is 1: 1 to 10.
Preferably, the mass ratio of the metal nitrate to the protein fiber base material is 1: 10-100, wherein the mass ratio of the rare earth ions or the mixed ions of the rare earth ions and the rare earth ions or the rare earth ions and the transition metal ions to the protein macromolecular ligand is 10: 1 to 10.
Compared with the prior art, the invention has the advantages and positive effects that,
1. the invention provides a preparation method of a rare earth MOFs protein fiber composite fluorescent sensing material, which utilizes a large number of active groups, such as carboxyl, hydroxyl, amino and the like, on the surface of a protein fiber to provide sites for reacting with an Ln-MOFs material. And simultaneously, pre-modifying the fiber substrate, and carrying out Atomic Layer Deposition (ALD) technical treatment on the fiber substrate assisted by a small-molecule polycarboxylic acid bridging ligand or the surface to regulate and control the binding force between the fiber substrate and Ln-MOFs and the morphology and the loading capacity of the nanocrystalline. The prepared Ln-MOFs/protein fiber functional composite crystalline material effectively realizes double regulation and control of structure and function, thereby realizing the application in the field of fluorescent sensing of pH value, temperature and micromolecules in human physiological environment.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive labor.
FIG. 1 is an SEM photograph of the Eu-MOFs/fibroin fiber composite provided in example 1;
FIG. 2 is a fluorescence spectrum of the Eu-MOFs/fibroin fiber composite provided in example 1 with respect to temperature;
FIG. 3 is an SEM image of the EuTb-MOFs/down powder composite provided in example 2;
FIG. 4 is a fluorescence spectrum of the EuTb-MOFs/down powder composite material provided in example 2 with respect to pH.
FIG. 5 is an SEM image of a EuMOFs/soy protein short fiber composite provided in example 3;
FIG. 6 is a graph showing the change of fluorescence intensity of the EuMOFs/soy protein short fiber composite material provided in example 3 in the presence of different interfering molecules.
Detailed Description
In order that the above objects, features and advantages of the present invention can be more clearly understood, the present invention will be further described with reference to the accompanying drawings and examples. It should be noted that the embodiments and features of the embodiments of the present application may be combined with each other without conflict.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced in other ways than those specifically described herein, and thus the present invention is not limited to the specific embodiments of the present disclosure.
The research shows that the protein fiber has the characteristics of excellent biocompatibility, biodegradability, self-assembly, mechanical stability and controllable structure and form, firstly, the biocompatibility and the biodegradability can meet the requirement of human body detection, the self-assembly, the mechanical stability and the controllable structure and form can provide a stable substrate, and meanwhile, the surface of the protein fiber has a large number of active groups, such as carboxyl, hydroxyl, amino and the like, and provides a site for reaction with the Ln-MOFs material. Further, the present invention is proposed to change the form of Ln-MOFs to satisfy conditions suitable for human body.
Example 1, this example provides a Eu-MOFs/fibroin fiber composite for human body temperature detection.
Firstly, silk fabric (of course, other silk fibroin, wool protein, cashmere protein, down feather protein, corn protein or soybean protein short fiber and one of the fabrics thereof can be replaced) is pretreated, and 3g of original silk fabric is treated by 0.5 percent NaHCO3And repeatedly cooking the solution for 15-30 min twice, wherein the main purpose of the step is to remove sericin on the silk fabric, then cooking the silk fabric for 15-30 min once by using a deionized water solution, then taking out the silk fabric, repeatedly washing the silk fabric by using deionized water, and airing the silk fabric at room temperature to obtain the degummed silk fabric.
Then, TiO with a nanometer layer thickness is deposited on the obtained silk fabric by using an atomic layer deposition technology (ALD)2A film, namely placing a silk fabric of 3cm multiplied by 3cm in a reaction cavity, adjusting the temperature to be 150 ℃, keeping each complete ALD cycle for 56.25s, and carrying out reaction treatment on the surface of the silk fabric for 100 rounds to obtain TiO modified by ALD2Silk fabric, TiO2And a large number of reaction sites of O atoms are provided, the O atoms are easy to coordinate with metal ions, particularly rare earth ions, and the subsequent layer-by-layer self-assembly of MOFs crystalline films on the surface of the silk fabric is facilitated.
Then, Eu (NO)3)3·6H2O (0.45mmol) and 2, 5-dihydroxyterephthalic acid (DHTA) (0.15mmol) were dissolved well in 10ml of H2And O, (protein macromolecular ligand can also be added simultaneously), adding the mixture into a 20ml hydrothermal reaction kettle, adjusting the pH to 8, and placing a piece of 1cm multiplied by 1cm silk fabric which is subjected to atomic layer deposition treatment for different numbers of cycles. And then placing the obtained product into an outer lining of a hydrothermal reaction kettle, placing the obtained product into a temperature control oven, heating the obtained product from room temperature to 60 ℃ for 30min, controlling the temperature at 60 ℃ for 24h, and then cooling the obtained product to room temperature for 24h to ensure that Eu-MOFs is fully crystallized, and performing layer-by-layer self-assembly on the surface of the silk fabric to prepare the Eu-MOFs silk fabric composite material for human fluorescence temperature detection.
Testing and detecting: as shown in figures 1 and 2, the diameter of the silk fiber degummed by figure 1 is about 3-5 μm, and a large amount of Eu-MOFs crystalline material grows on the surface of the silk fiber, and the crystal size is mostly nano-scale. And figure 2 is a fluorescence curve tested at the temperature of 0, 25 and 50 ℃ under the excitation wavelength of 360nm, a broad peak exists between 400 and 600nm in the curve, and is a result of compounding a Eu ion characteristic peak and a protein characteristic peak, and the fluorescence intensity of the peak is obviously weakened along with the rise of the temperature, so that the fluorescence temperature detection effect can be realized.
Embodiment 2, this embodiment provides a EuTb-MOFs down powder protein composite material for detecting PH of human body.
Firstly, pretreating eiderdown powder, and subjecting 3g of eiderdown powder to 50-80 deg.C and 0.5% NaHCO3Treating the solution for 30-50 min, soaking the down in a deionized water solution at 50-80 ℃ for 30min, taking out the down, repeatedly washing the down with the deionized water, and airing the down at room temperature to obtain the alkali-treated down powder, wherein the surface layer of the powder is more likely to form fibers.
Depositing Al with the thickness of a nanometer layer on the obtained down feather powder by using an Atomic Layer Deposition (ALD) technology2O3Film, 2g of down feather powder is placed in a reaction cavity, the temperature is adjusted to 130 ℃, 10 rounds of cyclic deposition are carried out, and Al modified by ALD is obtained2O3The down powder is beneficial to the self-assembly of the subsequent MOFs on the surface layer of the powder.
Eu (NO)3)3·6H2O (0.15mmol) and Tb (NO)3)3·6H2O (0.15mmol), fumaric acid (0.15mmol) and pyromellitic acid (0.15mmol) were sufficiently dissolved in 10ml of H2And adding the mixture into a 20ml hydrothermal reaction kettle, adjusting the pH value to 7, and placing 1.5g of down feather powder subjected to atomic layer deposition. And then placing the down feather powder into an outer lining of a hydrothermal reaction kettle, placing the down feather powder into a temperature control oven, raising the temperature from room temperature for 30min to 80 ℃, controlling the temperature at 80 ℃ for 12h, then lowering the temperature to room temperature for 24h, fully crystallizing the EuTb-MOFs, and self-assembling the EuTb-MOFs layer by layer on the surface of the down feather powder to prepare the EuTb-MOFs down feather powder composite material for fluorescent pH sensing detection.
Testing and detecting: as shown in fig. 3 and 4, Eu-MOFs crystalline material can be assembled on the surface layer of the down powder through fig. 3, and the size of the crystals is mostly nano-scale. In FIG. 4, the fluorescence curve with pH of 2.60-8.54 is tested under the excitation wavelength of 365nm, the curve has a broad peak between 400-470 nm and a 546nm positionOne corresponds to Tb (III)5D4→7F5The characteristic peak of transition, one at 617nm corresponds to Eu (III)5D0→7F2Characteristic peak of transition. It can be seen from the figure that the fluorescence intensities of the three peaks are all significantly enhanced with the increase of pH, so that the fluorescence pH detection effect can be realized.
Example 3, this example provides a Eu-MOFs/soy protein short fiber composite for dopamine detection.
Eu (NO)3)3·6H2O (0.45mmol) was dissolved in 5ml H2In O, cyclodextrin (0.15mmol) and soybean protein short fiber solution (20mg) were dissolved in 10ml of H sufficiently at the same time2In O, adjusting pH to 8, and stirring at room temperature to obtain Eu (NO)3)3·6H2And dripping the O aqueous solution into the mixed solution of cyclodextrin and soybean protein at the speed of 2d/s, and crystallizing and growing Eu-MOFs under the induction of protein to prepare the Eu-MOFs soybean protein short fiber composite material for human dopamine fluorescence detection.
Testing and detecting: as shown in FIGS. 5 and 6, it can be seen from FIG. 5 that the crystal size is about 200-300nm and has a certain shape, but the crystal edge angle is not as obvious as that of the small molecular MOFs because the protein macromolecules participate in the MOFs assembly, and in FIG. 6, at the excitation wavelength of 365nm, Eu (III)5D0→7F2The characteristic peak of the transition is compared. The interference molecules comprise Bovine Serum Albumin (BSA), KCl, NaCl, Glucose (GL), serine (Ser) and Dopamine (DA), the concentration of the added interference items is 1 x 10-5mol/L, and the graph shows that the fluorescence intensity of EuMOFs added with the interference items BSA, KCl, NaCl, GL and Ser has no obvious change compared with EuMOFs not added with the interference items, but the fluorescence intensity is sharply reduced after the dopamine is added, so that the detection effect of the fluorescent dopamine can be realized.
The above description is only a preferred embodiment of the present invention, and not intended to limit the present invention in other forms, and any person skilled in the art may apply the above modifications or changes to the equivalent embodiments with equivalent changes, without departing from the technical spirit of the present invention, and any simple modification, equivalent change and change made to the above embodiments according to the technical spirit of the present invention still belong to the protection scope of the technical spirit of the present invention.
Claims (10)
1. A preparation method of a rare earth MOFs protein fiber composite fluorescent sensing material is characterized by comprising the following effective steps:
a. fully dissolving nitrate and micromolecular organic ligand of rare earth ions or mixed ions of the rare earth ions and the rare earth ions or the rare earth ions and transition metal ions in H2O is in;
b. adding the mixture obtained in the step a into a hydrothermal reaction kettle, placing a protein fiber substrate material in the hydrothermal reaction kettle, and adjusting the pH value to be neutral or weakly alkaline;
c. and (3) putting the adjusted material into a temperature-controlled oven, heating the material from room temperature, controlling the temperature, and cooling the material to room temperature after the temperature control is finished, so that MOFs of rare earth ions or mixed ions of the rare earth ions and metal ions are fully crystallized, and the MOFs is self-assembled on the surface of the protein fiber substrate material layer by layer to prepare the rare earth MOFs protein fiber composite material of the rare earth ions or the mixed ions of the rare earth ions and transition metal ions.
2. The method for preparing rare earth MOFs protein fiber composite fluorescence sensing material according to claim 1, further comprising:
c1, pretreating the protein fiber substrate material, and using 0.5% NaHCO3Repeatedly cooking the solution twice, then cooking once by using a deionized water solution, then taking out, repeatedly washing by using deionized water, and airing at room temperature to obtain the degummed protein fiber substrate material;
c2, and then depositing a nano-layer thick TiO layer on the obtained protein fiber substrate material by using an atomic layer deposition technology2Or Al2O3And (3) forming a film to obtain the protein fiber substrate material modified by the atomic layer deposition technology.
3. The method for preparing a rare earth MOFs protein fiber composite fluorescence sensing material according to claim 1 or 2, wherein in the step c, the protein fiber substrate material is one of silk fibroin, wool protein, cashmere protein, down feather protein, corn protein or soybean protein short fiber and fabric thereof.
4. The method for preparing rare earth MOFs protein fiber composite fluorescent sensing material according to claim 1 or 2, wherein in the step a, the rare earth ions are Eu3+、Tb3+、Dy3+、Sm3+、La3+The rare earth ion in the mixed ion of rare earth ion and rare earth ion or rare earth ion and transition metal ion is Eu3+、Tb3+、Dy3+、Sm3+、La3+The transition metal ion is Cu2+、Zn2+、Fe3+、Mg2+、Al3+。
5. The preparation method of the rare earth MOFs protein fiber composite fluorescence sensing material according to claim 1 or 2, wherein in the step a, the small molecule organic ligand is a carboxylic acid, imidazole or heterocyclic small molecule ligand.
6. The method for preparing rare earth MOFs protein fiber composite fluorescent sensing material according to claim 1, wherein in the step a, nitrate of rare earth ions or mixed ions of rare earth ions and rare earth ions or rare earth ions and transition metal ions, small molecule organic ligands and protein macromolecular ligands are fully dissolved in H2And (4) in O.
7. The method for preparing a rare earth MOFs protein fiber composite fluorescent sensing material according to claim 6, wherein the protein macromolecule ligand is one of plant protein macromolecules such as soybean, corn and peanut or animal protein macromolecules such as silk and hairiness.
8. The method for preparing rare earth MOFs protein fiber composite fluorescence sensing material according to claim 1, 2 or 6, wherein the molar ratio of the rare earth ions or the mixed ions of the rare earth ions and the rare earth ions or the rare earth ions and the transition metal ions to the small molecule organic ligands is 1: 1 to 6.
9. The method for preparing rare earth MOFs protein fiber composite fluorescence sensing material according to claim 1, 2 or 6, wherein the molar ratio of rare earth ions to rare earth ions or rare earth ions to transition ions in the mixed metal ions is 1: 1 to 10.
10. The method for preparing a rare earth MOFs protein fiber composite fluorescence sensing material according to claim 1, 2 or 6, wherein the mass ratio of the metal nitrate to the protein fiber substrate material is 1: 10-100, wherein the mass ratio of the rare earth ions or the mixed ions of the rare earth ions and the rare earth ions or the rare earth ions and the transition metal ions to the protein macromolecular ligand is 10: 1 to 10.
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| CN112646191A (en) * | 2019-10-12 | 2021-04-13 | 中国科学院福建物质结构研究所 | Rare earth-organic framework nano fluorescent probe and preparation method and application thereof |
| CN111952010A (en) * | 2020-07-06 | 2020-11-17 | 陕西科技大学 | Flexible metal organic framework compound film and preparation method and application thereof |
| CN112755968A (en) * | 2020-12-31 | 2021-05-07 | 廊坊师范学院 | MOFs fiber membrane for adsorbing micro-nano plastics in trapped water and preparation method thereof |
| CN113121838A (en) * | 2021-03-31 | 2021-07-16 | 海南大学 | Method for preparing MOF/carbon composite material with assistance of atomic layer deposition, obtained product and application |
| CN113089310A (en) * | 2021-04-06 | 2021-07-09 | 郭碧叶 | Light anti-ultraviolet fabric and preparation method thereof |
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