CN114891232A - Cerium-terephthalic acid metal organic framework material and preparation method and application thereof - Google Patents
Cerium-terephthalic acid metal organic framework material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a cerium-terephthalic acid metal organic framework material and a preparation method and application thereof, wherein the preparation method comprises the following steps: and reacting cerium salt, terephthalic acid and soluble starch to obtain the CeBDC metal-organic framework material. The cerium-terephthalic acid metal organic framework material not only can be used as an internal standard type ratiometric fluorescent probe for detecting hydroxyl radicals in high-temperature harmful gas, but also can be used as a scavenger of the hydroxyl radicals for scavenging the hydroxyl radicals in the high-temperature harmful gas, and the probe has the characteristic of simultaneously realizing the detection and the scavenging of the hydroxyl radicals.
Description
Technical Field
The invention belongs to the field of nano medical device development, and particularly relates to a cerium-terephthalic acid metal organic framework material, and a preparation method and application thereof.
Background
Harmful gases generated by high temperature such as tobacco, automobile exhaust, factory exhaust and the like cause serious environmental pollution, and further threaten the health of human bodies. Hydroxyl radicals (. OH) are among the toxic substances widely present in harmful gases. Hydroxyl radicals have a strong oxidizing power and can cause irreversible damage to the human body. Furthermore, OH in hot gases can cause oxidative stress in humans, damage to lung tissues and immune system, and lead to various diseases such as lung cancer, pneumonia and chronic obstructive pulmonary disease (Small, Vol. 16, 1902123). Therefore, the development of an OH scavenger suitable for use in high-temperature harmful gases is urgently required. Although various antioxidants such as plant extracts, polyphenols, flavonoids and the like are reported to consume.OH, their application for removal of.OH from high temperature gas is limited (Analytical Chemistry, Vol.84, 6767-6774), and in order to overcome this disadvantage, catalytic antioxidants such as colloidal Fe having good thermal stability and high catalytic activity have been developed 3 O 4 WO coupled with nano-particles and Pt nano-particles 2.72 Nanosheet, cerium oxide (CeO) 2 ) Nanoparticles, etc., for removing OH (PLOS ONE, volume 9, e 90055; analytical and bioanalytic Chemistry, volume 412, 521-; the Journal of Physical Chemistry C, volume 115, 11-17). Among them, cerium oxide nanoparticles are most widely used because they have a cerium-containing structure derived from Ce 3+ Reversibly converted to Ce 4+ The key factor of (Advanced Functional Materials, volume 30, 2004692) makes the cerium oxide nanoparticles able to maintain their antioxidant activity for a long time, making them able to eliminate high temperature gasesThe harmful substances have potential application value. In order to obtain better OH elimination effect, the OH content in the high-temperature gas is detected while removing the OH. The current methods for detecting hydroxyl radicals mainly include UV-visible spectrophotometry (Analytical Chemistry, Vol. 87, 10719-&Interfaces, Vol.12, 36948-. Among them, fluorescence detection is an effective analytical test technique because of its weak dependence on instruments and high sensitivity. In particular, ratiometric fluorescence analysis, due to its inherent properties, has received a great deal of attention because it can eliminate false signals due to environmental influences, thereby further improving sensitivity and detection accuracy. However, the combination of fluorescence detection and. OH elimination in high temperature gas systems is quite challenging, since most detection probes are less heat resistant (Chemical Communications, Vol. 54, 4329-. For example, Terephthalic Acid (TA) is widely used in many fields for the detection of.OH, since it reacts with OH to produce 2-hydroxyterephthalic acid, which is a fluorescent product, however, TA rapidly decomposes once the temperature exceeds 300 ℃,
so that its detection in high temperature gases is limited. Therefore, there is a need to improve the heat resistance of fluorescent probes while achieving the detection and elimination of OH at high temperatures.
In light of this, the present application seeks to develop cerium-coordinated-terephthalate CeBDC MOFs with dual functions of fluorescence detection and scavenging of OH in hot gases. Similar to cerium oxide nanoparticles, Ce-O coordination bonds and oxygen vacancies formed in CeBDC MOFs confer them on Ce 3+ And Ce 4+ The ability to reversibly transform between. When interacting with. OH, Ce 3+ The resulting fluorescence at 355 nm was almost unchanged due to Ce in the CeBDC MOFs 3+ And Ce 4+ In proportion toIt is kept in a dynamic balance. While TA in the CeBDC MOFs can react with OH to produce a fluorescent product, resulting in an increase in fluorescence intensity at 440 nm, the CeBDC MOFs can be used for ratiometric fluorometric analysis of OH, where TA is the responsive fluorophore, Ce 3+ As an internal standard fluorophore, the OH detection method has higher sensitivity and excellent selectivity. In addition, The unique coordination structure allows CeBDC MOFs to have a high degree of thermal stability, making it possible to simultaneously detect and eliminate OH in high temperature harmful gases (The Journal of Physical Chemistry C, Vol.115, 4433-.
Disclosure of Invention
Based on the technical problems, the invention provides a cerium-terephthalic acid metal organic framework material, and a preparation method and application thereof, wherein the cerium-terephthalic acid metal organic framework material can be used as an internal standard type ratio fluorescence probe for detecting hydroxyl radicals in high-temperature harmful gas, can also be used as a scavenger of the hydroxyl radicals for removing the hydroxyl radicals in the high-temperature harmful gas, and has the characteristic of simultaneously realizing the detection and removal of the hydroxyl radicals.
Based on the purpose, the invention adopts the following technical scheme:
a method for preparing cerium-terephthalic acid nanoparticles comprises the following steps:
under the protective atmosphere, dispersing cerium salt in a soluble starch water solution to obtain a cerium salt and soluble starch mixed solution; dispersing terephthalic acid and sodium hydroxide in water, then adding the mixture into the mixed solution of the cerium salt and the soluble starch, standing for 20-30 h, centrifuging, and washing to obtain the cerium-terephthalic acid metal-organic framework material.
Further, the soluble starch takes part in the reaction in the form of aqueous solution, the mass fraction of the aqueous solution of the soluble starch is 0.05-0.1%, and 20 mL of the aqueous solution of the soluble starch with the mass fraction of 0.05-0.1% is needed for every 0.1 mmol of the cerium salt.
Further, the cerium salt is selected from cerium acetate, cerium nitrate, cerium chloride, or a hydrate corresponding to one of the above-listed cerium salts.
Further, the molar ratio of the cerium salt, terephthalic acid and sodium hydroxide is (0.8-1.2) to 1 (1.8-2.5).
Preferably, the specific process is as follows: under the protection of inert gas, 0.1 mmol of cerium acetate is dispersed in 20 mL of soluble starch water solution with the mass percent of 0.08%, the mixture is stirred for 10-30 min, then 1mmol of terephthalic acid and 2.5mmol of sodium hydroxide are dispersed in 10 mL of distilled water, 1 mL of the solution is dropwise added into the mixed solution of the cerium acetate and the starch at the temperature of 60 +/-5 ℃, the mixture is stirred for 1-2 h, and then the solution is kept stand for 20-30 h, centrifuged and washed, so that the product is obtained.
The cerium-terephthalic acid metal-organic framework material prepared by the preparation method.
The cerium-terephthalic acid metal-organic framework material is represented by CeBDC MOFs.
When the cerium-terephthalic acid metal-organic framework material meets hydroxyl free radicals, on one hand, due to the existence of oxygen vacancies, Ce in CeBDC MOFs 3+ And Ce 4+ Is maintained in a dynamic equilibrium, Ce 3+ The generated fluorescence intensity at 355 nm is hardly changed, while TA in CeBDC MOFs can react with OH to generate a fluorescence product, so that the fluorescence intensity at 440 nm is increased, and ratio type fluorescence detection of hydroxyl free radicals is realized, and the detection method has higher sensitivity and excellent selectivity, wherein TA is used as a response fluorophore, Ce 3+ As an internal standard fluorophore; on the other hand, Ce 3+ And Ce 4+ The reversible conversion realizes the efficient removal of hydroxyl free radicals, and breaks through the limitation that the traditional technology can only detect or remove OH independently. And the composition is successfully applied to cigarette filters, so that acute lung injury of mice caused by oxidative stress can be reduced.
The second purpose of the invention is to provide the application of the cerium-terephthalic acid metal-organic framework material or the cerium-terephthalic acid metal-organic framework material prepared by the method in preparing a probe for detecting hydroxyl radicals in high-temperature harmful gas.
The third purpose of the invention is to provide the application of the cerium-terephthalic acid metal-organic framework material or the cerium-terephthalic acid metal-organic framework material prepared by the method in the preparation of a hydroxyl radical scavenger in high-temperature harmful gas.
Preferably, when the cerium-terephthalic acid metal organic framework material is used as an internal standard type ratiometric fluorescent probe for detecting hydroxyl radicals in an aqueous solution or high-temperature harmful gas, the temperature of the gas is 70-230 ℃, the temperature of the solution is 20-80 ℃, and the pH range for detection is 5.7-7.4.
Preferably, when the cerium-terephthalic acid metal organic framework material is used as a hydroxyl radical scavenger for scavenging hydroxyl radicals in an aqueous solution or high-temperature harmful gas, wherein the temperature of the gas is 70-230 ℃, the temperature of the solution is 20-80 ℃, and the pH range for scavenging is 3-7.
The invention also provides a kit, which contains the cerium-terephthalic acid metal-organic framework material or the cerium-terephthalic acid metal-organic framework material prepared by the method.
In addition, the invention also provides a method for detecting hydroxyl radicals in high-temperature harmful gas, which comprises the following steps:
by analyzing the content of hydroxyl radicals (.OH) in high-temperature gas generated after the combustion of cigarettes or the engine oil loaded by using wood fibers as a carrier, the feasibility of detecting the hydroxyl radicals (.OH) in the high-temperature harmful gas by using CeBDC MOFs as a ratiometric fluorescent probe can be evaluated. The hot noxious gases generated by the different samples were collected in a home-made glass apparatus and contacted with a CeBDC MOFs solution. After 30 min of interaction, fluorescence spectra of CeBDC MOFs were tested and the detection results of hydroxyl radicals were calculated by standard line.
In addition, the invention also provides a method for removing hydroxyl radicals in high-temperature harmful gas, which comprises the following steps:
taking a cigarette as an example, CeBDC MOFs is used for removing OH from high-temperature gas generated by the combustion of the cigarette. The effect of removing OH from cigarette smoke was first examined by loading the CeBDC MOFs into a cigarette filter, then the smoke passing through the cigarette filter loaded with the CeBDC MOFs was passed into the MB solution, after one cigarette was completely combusted, the absorbance of the solution was tested and the removal of OH was calculated according to the following formula.
Elimination (%) = [(A 1 -A 2 )/(A 0 -A 2 )]×100%
Wherein A is 0 Is the absorbance at MB 664 nm, A 1 And A 2 The absorbances at 664 nm after the reaction between the smoke produced by the combustion of cigarettes loaded and unloaded with CeBDC MOFs in the filter and MB, respectively.
Compared with the prior art, the invention has the following beneficial effects:
the cerium-terephthalic acid metal-organic framework material utilizes Ce 3+ And terephthalic acid are coordinated and self-assembled to prepare CeO-like 2 Functional metal-organic framework materials, in the presence of oxygen vacancies, via Ce 3+ And Ce 4+ Can effectively remove hydroxyl free radicals in high-temperature gas, and meanwhile, Ce 3+ Can be used as an internal standard fluorophore, and terephthalic acid is used as a hydroxyl radical response fluorophore, so that the ratio type fluorescence detection of the hydroxyl radical is realized, and the limitation that the traditional technology can only detect or remove OH independently is broken through; and the composition is successfully applied to cigarette filters, so that acute lung injury of mice caused by oxidative stress can be reduced.
In the preparation method, the soluble starch has the following functions: the morphology of CeBDC MOFs can be regulated and controlled.
Drawings
FIG. 1 is a schematic diagram of the working principle of the CeBDC MOFs prepared by the present invention and the application thereof;
FIG. 2 is SEM images (a, b, c) and TEM images (d) of CeBDC MOFs prepared in example 1 of the present invention;
FIG. 3 is an XRD pattern of CeBDC MOFs prepared in example 1 of the present invention;
FIG. 4 is a graph of the thermal stability of CeBDC MOFs prepared in example 1 of the present invention;
FIG. 5 is a graph of the clearance of hydroxyl radicals at different temperatures and pH in aqueous solutions of CeBDC MOFs prepared in example 1 of the present invention;
FIG. 6 is a graph of the detection of hydroxyl radicals at different temperatures and pH in aqueous solutions for CeBDC MOFs prepared in example 1 of the present invention;
FIG. 7 shows the fluorescence intensity ratio of CeBDC MOFs prepared in example 1 of the present invention in the presence of different metal ions, saccharides and organic molecules;
FIG. 8 is a graph of the removal rate of CeBDC MOFs prepared in example 1 of the present invention in high temperature harmful gases;
FIG. 9 is a diagram of hydroxyl radical detection in high temperature harmful gases by CeBDC MOFs prepared in example 1 of the present invention;
FIG. 10 is a graph showing the effect of CeBDC MOFs prepared in example 1 of the present invention on the body weight of mice in a mouse model;
FIG. 11 is a graph showing the lung tissue and H & E staining of mice in a mouse model to which CeBDC MOFs prepared in comparative example 1 of the present invention was applied;
FIG. 12 is a graph showing the effect of CeBDC MOFs prepared in example 1 of the present invention on the conventional blood of mice in a mouse model;
FIG. 13 is a graph showing the effect of CeBDC MOFs prepared in example 1 of the present invention on mouse inflammatory factors when applied to a mouse model.
Detailed Description
Hereinafter, the technical solution of the present invention will be described in detail by specific examples, but these examples should be explicitly proposed for illustration, but should not be construed as limiting the scope of the present invention.
Example 1
A preparation method of a cerium-terephthalic acid metal organic framework material comprises the following specific steps:
under the protection of inert gas argon (Ar), 0.1 mmol of cerium acetate (Ce (CH) is taken 3 COO) 3 ) (31.725 mg) was dispersed in 20 mL of a 0.08% by mass aqueous solution of soluble starch (national pharmaceutical group chemical Co., Ltd.) and stirred for 30 min; 1mmol of terephthalic acid (C) 8 H 6 O 4 ) (166 mg) was dispersed in 10 mL of distilled water together with 2.5mmol of sodium hydroxide (NaOH) (100 mg), and 1 mL of this solution was added dropwise to the above mixture of cerium acetate and starch at 60 ℃And (3) mixing the solution, stirring for 2 h, standing the solution for 24 h, and finally centrifuging and washing to obtain a product, namely CeBDC MOFs.
The CeBDC MOFs prepared in example 1 were tested, and the test results are as follows:
1. SEM and TEM testing
SEM and TEM tests were performed on the CeBDC MOFs prepared in example 1, and the results are shown in FIG. 2.
Wherein, a, b and c in FIG. 2 are SEM images of CeBDC MOFs; d in FIG. 2 is a TEM image of CeBDC MOFs;
as can be seen from fig. 2, the prepared CeBDC MOFs are composed of laminated sheet-like structural units, forming a "feathered" wing structure. The special structure can realize high contact area between MOFs and harmful gases, thereby being beneficial to removing ROS in high-temperature harmful gases.
2. XRD test
XRD testing (λ =1.5418 a) was performed on the CeBDC MOFs prepared in example 1 and the results are shown in fig. 3.
The X-ray diffraction (λ =1.5418 a) pattern (fig. 3) of the product shows that all diffraction peak positions correspond to the diffraction planes of cerium-terephthalic acid, respectively, showing that the product is cerium-terephthalic acid.
3. Thermal stability testing
The thermal stability of the CeBDC MOFs and TA prepared in example 1 was examined by a synchronous thermal analyzer after drying, and the results are shown in fig. 4.
As can be seen from FIG. 4, the product has a certain weight loss between 100 ℃ and 400 ℃, and compared with TA, the thermal stability of CeBDC MOFs is due to Ce 3+ The coordination with TA is greatly improved, and the characteristic is very important for the application of CeBDC MOFs in high-temperature harmful gases.
4. Scavenging of hydroxyl radicals at different temperatures and pH in aqueous solution
The efficiency of CeBDC MOFs in water solution at different temperatures and pH for scavenging OH was studied under optimized conditions using MB as indicator for OH. First, OH is substituted by Fe 2+ /H 2 O 2 Production of (Fe) by the Fenton System 2+ And H 2 O 2 All at a concentration of 0.2 mM), followed by preparing hydrochloric acid solutions of different pH at different temperatures (20 deg.C, 37 deg.C, 40 deg.C, 50 deg.C, 60 deg.C, 70 deg.C and 80 deg.C) and pH (3, 4, 5, 6, 7), and adding FeSO 4 And commercially available hydrogen peroxide to make Fe 2+ And H 2 O 2 All the concentrations of the components are 0.2 mM), reacting with CeBDC MOFs (the final concentration of the CeBDC MOFs in the solution is 100 mug/mL) for 3 min, adding MB (the final concentration of the MB is 10 mug/mL) after the reaction is finished, and testing the light absorption intensity of the solution to be tested by an ultraviolet visible spectrophotometer to determine the removal rate of OH. OH clearance is calculated by the following formula:
Elimination (%) = [(A 1 -A 2 )/(A 0 -A 2 )]×100%
wherein A is 0 Is the absorbance of MB, A 1 And A 2 The absorbance of the adduct formed by the reaction of MB with OH in the presence and absence of CeBDC MOFs at 664 nm, respectively.
The clearance of hydroxyl radicals at different temperatures and pH is shown in FIG. 5.
As can be seen from a in FIG. 5, even under the high temperature environment of 80 ℃, the CeBDC MOFs can still keep 90% of high OH scavenging efficiency, which indicates that the CeBDC MOFs have higher thermal stability in the range of 20 ℃ to 80 ℃ and can effectively scavenge hydroxyl radicals.
As can be seen from b in figure 5, at different pH values, the clearance of OH was well achieved for CeBDC MOFs, which was also found to be the optimum pH = 7. The above results indicate that CeBDC MOFs can scavenge OH over a wide pH range, and have high thermal stability for further applications.
5. Detection of hydroxyl radicals at different temperatures and pH in aqueous solution
FeSO 4 The concentration was kept constant at 0.2 mM by varying the H addition 2 O 2 To control the amount of hydroxyl radicals generated, and then, the CeBDC MOFs (particles) prepared in example 1 were addedFinal concentration in solution 100. mu.g/mL), reacted sufficiently for 30 min at different temperature gradients (20 ℃, 37 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃), measured the fluorescence spectrum of the excitation wavelength 315 nm by a fluorescence spectrophotometer, recorded the fluorescence intensities at the emission wavelengths of 355 nm and 440 nm, and calculated the fluorescence intensity Ratio (Ratio = I) 440 nm /I 355 nm ) Drawing a standard line of hydroxyl radical detection and calculating the detection limit, and detailing the result in a in fig. 6.
Mixing Fe 2+ /H 2 O 2 The pH of the Fenton system was adjusted to pH =5.7, 6.2 and 7.4 with 0.01 mol/L phosphate buffer solution, respectively. Then, FeSO 4 The concentration was kept constant at 0.2 mM by varying the H addition 2 O 2 To control the amount of hydroxyl radicals generated, CeBDC MOFs (particle concentration of 100. mu.g/mL) prepared as described in example 1 was added, the reaction was sufficiently carried out for 30 min in a phosphate buffer solution having pH values of 5.7, 6.2 and 7.4, respectively, fluorescence spectra at an excitation wavelength of 315 nm were measured by a fluorescence spectrophotometer, fluorescence intensities at emission wavelengths of 355 nm and 440 nm were recorded, and a fluorescence intensity Ratio was calculated (Ratio = I) 440 nm /I 355 nm ) The above results are shown in b of FIG. 6.
As can be seen from a in FIG. 6, at different temperatures, good linear relations are established between the fluorescence intensity ratios of the CeBDC MOFs probe to Fenton reagents with different concentrations and the Fenton system concentration, and the detection of hydroxyl radicals can be realized at 20-80 ℃. The above results indicate that CeBDC MOFs are expected to be rate-type fluorescent probes for detecting. OH at high temperatures.
As can be seen from b in FIG. 6, the fluorescence intensity ratio (I) at different pH values 440nm /I 355nm ) With Fenton reagent concentration (from 0 to 0.1 mM H 2 O 2 And a fixed concentration of Fe 2+ Composition), and proves the advantages of ratio detection, interference signals caused by environmental influence can be corrected through the ratio of the two signals, so that the sensitivity and the accuracy of detection are improved. These results indicate that CeBDC MOFs are applicable to a wide pH range of pH = 5.0-7.0And detecting OH in the enclosure.
6. Detection of interference rejection
The CeBDC MOFs prepared in the example 1 is dispersed in 2 mL of aqueous solution to obtain a sample to be tested with the CeBDC MOFs concentration of 100 mug/mL, and Na is respectively added + 、Ca 2+ 、K + 、Mg 2+ 、NH 4 + 、H 2 PO4 - 、Br - 、SO 4 2- 、F - 、Cl - Oxalic acid, lactic acid, acetic acid, lysine, citric acid, glucose, fructose and sucrose (final concentrations of interfering ions were all 20 mM) were incubated with CeBDC MOFs at 80 ℃. After the reaction is carried out for 30 min, the solution to be detected is analyzed by fluorescence spectroscopy. The selectivity of CeBDC MOFs was explored. The results are shown in FIG. 7.
As can be seen from FIG. 7, the fluorescence intensity ratio (I) of CeBDC MOFs 440 nm /I 355 nm ) There was no significant change in interaction with any of the interfering substances described above. The results demonstrate that CeBDC MOFs has high selectivity for the detection of OH as a ratiometric fluorescent probe.
7. Removal of hydroxyl radicals from high-temperature harmful gases
The CeBDC MOFs prepared in example 1 were subjected to removal of OH from hot gases generated by combustion of wood fibers and engine oil, respectively, in a cigarette (Shanghai tobacco company, Central and south China sea cigarette, length: 9 cm, diameter: 1 cm, the same applies hereinafter). The CeBDC MOFs are respectively loaded in a cigarette filter (the loading amount is 50 mg/count), wood fibers (50 mg CeBDC MOFs are loaded in every 1g wood fibers), or engine oil using wood fibers as carriers (0.1 g wood fibers +50 mg CeBDC MOFs +1 mL or 1.5 mL or 2 mL engine oil), the ignition is carried out, and the combustion temperatures of the cigarette, the wood fibers and the engine oil using the wood fibers as carriers are respectively 70-80 ℃, 90-100 ℃ and 180-220 ℃ measured by an infrared thermometer. Then, smoke generated by burning a cigarette filter, wood fiber or engine oil using wood fiber as a carrier, which is loaded/unloaded with CeBDC MOFs, is respectively introduced into 5 mL of 10 mug/mL MB solution, after the smoke is completely burnt, the absorbance of the solution is respectively tested, and the effect of the CeBDC MOFs on removing OH in the smoke generated by burning is examined. The results are shown in FIG. 8.
As can be seen in FIG. 8, CeBDC MOFs has a 65.0% removal efficiency for.OH in cigarette smoke, and the corresponding removal efficiencies for wood fibers and wood fiber-based engine oils are about 40% and over 50%, respectively.
8. Detection of hydroxyl free radicals in high-temperature harmful gas
By analyzing the content of.OH in cigarettes or high-temperature gases generated after combustion of engine oil (0.1 g of wood fiber +1 mL or 1.5 mL or 2 mL of engine oil) loaded by wood fiber as a carrier, the feasibility of CeBDC MOFs as a ratiometric fluorescent probe for detecting the.OH in the high-temperature harmful gases can be evaluated. The hot gases generated by the different samples were collected in a home-made glass apparatus and contacted with 5 mL of aqueous solution of CeBDC MOFs (100 μ g/mL) formulated. After 30 min of interaction, fluorescence spectra of the CeBDC MOFs were tested under light excitation at 315 nm. The results are detailed in FIG. 9.
As can be seen from FIG. 9, CeBDC MOFs can detect hydroxyl radicals in cigarette or high-temperature harmful gas generated by burning engine oil loaded with wood fiber as carrier, and can roughly calculate the concentration of OH in actual samples according to the linear standard regression equation for detecting hydroxyl radicals in aqueous solution.
9. Effect of cigarette Smoke on mouse body weight
Mice were randomly divided into three groups of 5 mice each, group 1: a control group; group 2: cigarettes + CeBDC MOFs group (each cigarette loaded with CeBDC MOFs 50 mg); group 3: and (3) cigarette groups, namely placing the grouped mice in a glass container provided with a self-made air extractor. Mice in group 1 received no treatment of cigarette smoke, groups 2 and 3 were experimental groups, and smoke was introduced into the glass container through the cigarette filter loaded and unloaded with CeBDC MOFs prepared in example 1. Mice, packed in glass containers, were exposed to smoke from four cigarettes per day, a process which was repeated 10 times in two weeks. Each time the mouse was exposed to smoke from half a cigarette, the mouse was removed from the container for 15 min to breathe fresh air. After two weeks, the final body weights of three groups of mice were weighed. The results are shown in FIG. 10.
As can be seen from fig. 10, the mice in the cigarette group gained much less weight than normal mice in the control group, while the mice in the cigarette + CeBDC MOFs group gained significantly more weight than the cigarette group. These results preliminarily indicate that modification of cigarettes with CeBDC MOFs can compensate for the damage that cigarette smoke causes to mice.
10. Effect of cigarette Smoke on mouse Lung tissue
All mice were sacrificed and lung tissue was collected for histopathological evaluation. For histopathological evaluation, the right lung lobes of each group were collected by tracheal perfusion and fixed by washing with 10% paraformaldehyde. The fixed lung tissue was then embedded in paraffin, cut into sections of 4 mm thickness, stained with H & E, and examined for pathological changes under an optical microscope. The results are shown in detail in FIG. 11.
As can be seen from fig. 11, the lung tissues of the control and cigarette + CeBDC MOFs mice appeared healthy red, while the lung tissues of the cigarette mice appeared dark red. In vitro lungs were analyzed by hematoxylin-eosin (H & E) staining. The mice in the cigarette group showed severe lung injury compared to the normal group, and significant thickening of the bronchial capillary walls of the lung tissue was seen, with signs of neutrophil and lymphocyte infiltration. Whereas the pathological changes in lung tissues were not significant in mice of the cigarette + CeBDC MOFs group. The above results indicate that OH in cigarette smoke does not induce oxidative stress without CeBDC MOFs treatment, resulting in lung injury. And after the cigarette filter is modified by using CeBDC MOFs, OH in cigarette smoke can be effectively removed when the cigarette smoke passes through the filter, and the damage to lung tissues caused by the OH can be prevented.
11. Effect of cigarette Smoke on mouse blood routine
Mouse venous blood was collected for routine blood testing, and for blood routine testing, 20. mu.L of mouse blood was taken from the tail vein and added to a diluent prepared in advance, and the blood routine of the mouse was tested with a fully automatic animal blood analyzer. The results are shown in FIG. 12.
As can be seen from fig. 12, the White Blood Cell (WBC) count and Lymphocyte (LY) count of the cigarette group mice were significantly higher than those of the control group mice. Whereas the White Blood Cell (WBC) count and Lymphocyte (LY) count of mice from the cigarette + CeBDC MOFs group decreased correspondingly.
12. Effect of cigarette Smoke on proinflammatory cytokines in mice
The left lung of each mouse was weighed and homogenized at 4 ℃ in 50 mg/mL PBS buffer, the homogenate was centrifuged at 3000 rpm for 15 min at 4 ℃, the supernatant collected, and the proinflammatory cytokines 1L-1 β and TNF- α in the lung homogenate were measured using a commercial ELISA kit for IL-1 β and TNF- α (Solarbio, China). The results are shown in FIG. 13.
As can be seen in FIG. 13, the lung tissue of mice in the cigarette group had significantly increased inflammatory cytokines (including TNF-. alpha.and IL-1. beta.) compared to the control group, while the lung tissue of mice in the cigarette + CeBDC MOFs group had significantly reduced inflammation and the levels of TNF-. alpha.and IL-1. beta. in the lung tissue were also relatively decreased.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (9)
1. A preparation method of a cerium-terephthalic acid metal-organic framework material is characterized by comprising the following steps:
under the protective atmosphere, dispersing cerium salt in a soluble starch water solution to obtain a cerium salt and soluble starch mixed solution; dispersing terephthalic acid and sodium hydroxide in water, then adding the mixture into the mixed solution of the cerium salt and the soluble starch, standing for 20-30 h, centrifuging, and washing to obtain the cerium-terephthalic acid metal-organic framework material.
2. The method of claim 1, wherein the mass fraction of the aqueous soluble starch solution is 0.05-0.1%, and 20 mL of the aqueous soluble starch solution with the mass fraction of 0.05-0.1% is required for every 0.1 mmol of the cerium salt.
3. The method of claim 1, wherein the cerium salt is selected from the group consisting of cerium acetate, cerium nitrate, cerium chloride, or a hydrate corresponding to one of the above listed cerium salts.
4. The method of claim 1, wherein the molar ratio of cerium salt, terephthalic acid, and sodium hydroxide is (0.8-1.2): 1 (1.8-2.5).
5. A cerium-terephthalic acid metal-organic framework material obtainable by the process according to any one of claims 1 to 4.
6. Use of the cerium-terephthalic acid metal organic framework material according to claim 5 in the preparation of a hydroxyl radical scavenging and detecting probe.
7. The use according to claim 6, wherein the cerium-terephthalic acid metal organic framework material is used as an internal standard type ratiometric fluorescent probe for detecting hydroxyl radicals in an aqueous solution or in a high-temperature harmful gas, the temperature of the aqueous solution is 20-80 ℃, the temperature of the gas is 70-230 ℃, and the pH value applicable to detection is 5-7.4.
8. The use according to claim 6, wherein the cerium-terephthalic acid metal organic framework material is used as a hydroxyl radical scavenger for scavenging hydroxyl radicals in an aqueous solution or in a high-temperature harmful gas, wherein the temperature of the aqueous solution is 20-80 ℃, the temperature of the gas is 70-230 ℃, and the pH value for scavenging is 3-7.
9. A kit comprising the cerium-terephthalic acid metal-organic framework material of claim 5 or the cerium-terephthalic acid metal-organic framework material prepared by the method of any one of claims 1 to 4.
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| JP2018040639A (en) * | 2016-09-06 | 2018-03-15 | 国立大学法人 大分大学 | Composition and device for detecting hydroxyl radical, and method for detecting hydroxyl radical by using composition |
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| CN103776808A (en) * | 2014-01-24 | 2014-05-07 | 鼎泰（湖北）生化科技设备制造有限公司 | Method for detecting hydroxyl radical concentration |
| JP2018040639A (en) * | 2016-09-06 | 2018-03-15 | 国立大学法人 大分大学 | Composition and device for detecting hydroxyl radical, and method for detecting hydroxyl radical by using composition |
| CN108192110A (en) * | 2018-02-26 | 2018-06-22 | 南昌大学 | Preparation method and its trivalent arsenic the detection application of rare earth metal organic frame fluorescence probe |
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