CN112067593B - Preparation and detection method of Tb-MOF fluorescent material for rapidly detecting thiabendazole in navel orange - Google Patents
Preparation and detection method of Tb-MOF fluorescent material for rapidly detecting thiabendazole in navel orange Download PDFInfo
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- 229960004546 thiabendazole Drugs 0.000 title claims abstract description 66
- WJCNZQLZVWNLKY-UHFFFAOYSA-N thiabendazole Chemical compound S1C=NC(C=2NC3=CC=CC=C3N=2)=C1 WJCNZQLZVWNLKY-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000004308 thiabendazole Substances 0.000 title claims abstract description 63
- 235000010296 thiabendazole Nutrition 0.000 title claims abstract description 63
- 239000000463 material Substances 0.000 title claims abstract description 31
- 238000001514 detection method Methods 0.000 title claims abstract description 20
- 240000002319 Citrus sinensis Species 0.000 title claims abstract description 17
- 235000005976 Citrus sinensis Nutrition 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims abstract description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 6
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- MCWXGJITAZMZEV-UHFFFAOYSA-N dimethoate Chemical compound CNC(=O)CSP(=S)(OC)OC MCWXGJITAZMZEV-UHFFFAOYSA-N 0.000 description 2
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- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
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- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
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- 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
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6402—Atomic fluorescence; Laser induced fluorescence
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- 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
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- 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
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
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Abstract
The invention relates to the technical field of fluorescence chemical sensors, in particular to a preparation method and a detection method of a Tb-MOF fluorescent material for rapidly detecting thiabendazole in navel orange, wherein the Tb-MOF fluorescent material is prepared from UiO-66- (COOH)2And Tb (NO)3)3·6H2Prepared from O, Tb3+The @ MOF is used as a fluorescent sensor for detecting thiabendazole, and is used for detecting thiabendazole in navel oranges by combining a rapid, simple, cheap, efficient, stable and safe (QuEChERS) sample pretreatment method, so that the good sensing performance is shown, the wide linear range (0-80 mu M), the high selectivity, the low detection line (0.271 mu M) and the rapid response time (less than 1min) are included, and the probe can be used for detecting thiabendazole in navel orange samples and has good recovery rate (98.14-104.48%).
Description
Technical Field
The invention relates to the technical field of fluorescence chemical sensors, in particular to a preparation method and a detection method of a Tb-MOF fluorescent material for rapidly detecting thiabendazole in navel oranges.
Background
Thiabendazole (TBZ), a benzimidazole pesticide, has been widely used as a disease-controlling pesticide and fungicide during storage or transportation to protect fruits and vegetables from rot, mildew and blight. Due to the benzimidazole ring, thiabendazole is very stable even in different food preparation regimes, including cooking, pasteurisation and brewing. It is reported that thiabendazole has a half-life of 933 days in soil and is stable for 12-28 months in frozen crops. The result is that the residues of thiabendazole enter the food chain and water body through various environmental sources and may have adverse effects on human health, such as hepatotoxicity, nephrotoxicity, teratogenicity and carcinogenicity. The American Environmental Protection Agency (EPA) stipulates that the maximum residual limit of thiabendazole in citrus fruits and vegetables is 5mg/Kg (about 25 μ M), and the maximum residual limit of citrus fruits is 10mg/Kg (about 50 μ M) according to the national standards for food safety in China. Therefore, it is urgently needed to research a rapid, high-selectivity and high-sensitivity method for detecting thiabendazole in real samples, however, the actual samples have complex matrixes, so that the thiabendazole in the samples is difficult to detect.
The conventional techniques for qualitative and quantitative detection of thiabendazole in food samples are high performance liquid chromatography, liquid chromatography tandem mass spectrometry and gas chromatography tandem mass spectrometry. In recent years, there have been some emerging ways to detect thiabendazole, such as: electrochemical sensing, molecular imprinting techniques and surface enhanced raman techniques have been developed for the detection of thiabendazole in real samples. However, these methods have some disadvantages, including the need for sophisticated and expensive instrumentation, cumbersome sample pre-treatment procedures, the need for skilled operators, poor electrochemical activity, etc., which limit further practical applications. Therefore, there is an urgent need for a simple method for highly selective, sensitive and quantitative determination of thiabendazole in real food samples.
Currently, fluorescent chemical sensors not only have high selectivity and sensitivity, but also are very economical and simple, and thus have received great attention. Metal-organic frameworks (MOFs), a new and important class of multifunctional hybrid porous materials, have proven to be promising fluorescent probes due to the modifiable or adjustable pore structure to optimize the fluorescent response. Among the various fluorescent probes based on MOF, lanthanide luminescent MOFs (Ln-MOFs) have special properties because they have excellent photophysical properties, where luminescence may come from Ln3+Characteristic emission of ions, ligand-metal charge transfer transitions or other dimensionsAnd (4) a light emitting function. Over the years, some lanthanide luminescent MOFs were used as fluorescent sensors to detect metal ions, explosives, drugs, etc., however, only a few examples are fluorescent probes to detect thiabendazole.
Disclosure of Invention
The invention aims to provide a preparation method and a detection method of Tb-MOF fluorescent material for rapidly detecting thiabendazole in navel orange, Tb3+@UiO-66-(COOH)2The method is used as a fluorescent sensor for detecting thiabendazole, and the time for detecting thiabendazole in navel oranges is shortened by combining a rapid, simple, cheap, efficient, stable and safe (QuEChERS) sample pretreatment method.
In order to achieve the above object, the present invention provides a Tb-MOF fluorescent material, wherein the Tb-MOF fluorescent material is a material formed by UiO-66- (COOH)2And Tb (NO)3)3·6H2And O.
Preferably, the preparation of the Tb-MOF fluorescent material comprises the following steps:
(1) preparation of MOF
Reacting ZrCl4And pyromellitic acid in H2Performing first reflux at 100 ℃ in O, performing centrifugal collection after the reaction is finished, performing second reflux at 100 ℃ to remove unreacted pyromellitic acid, performing centrifugal collection on precipitates, soaking for 3 days by using methanol, replacing fresh methanol every day, adding acetone for solvent exchange, and finally drying in an oven at 60 ℃ for 12 hours to obtain an MOF material, wherein the MOF material is UiO-66- (COOH)2；
(2) Preparation of Tb-MOF
Mixing the MOF material prepared in step (1) with Tb (NO)3)3·6H2O is dispersed in H2Heating O to 60 deg.C, stirring for reaction, centrifuging, collecting, and adding H2And washing with O for three times, washing with acetone for three times, and drying at 60 ℃ for 12 hours to obtain the Tb-MOF material.
Preferably, in the step (1), ZrCl is added4The amount of the compound is 0.9228g, and the amount of the pyromellitic acid is 1.7208 g.
Preferably, the time for the first reflux in the step (1) is 24 hours, and the time for the second reflux is 12 hours.
Preferably, in step (2), the amount of MOF material used is 0.5003g, Tb (NO)3)3·6H2The amount of O used was 2.2692 g.
Preferably, the Tb-MOF fluorescent material is used for rapidly detecting thiabendazole in food.
Preferably, the detection method comprises the following steps: and adding the Tb-MOF fluorescent material into the pretreated sample to be tested, carrying out ultrasonic treatment for 5min, and then carrying out fluorescence test.
Preferably, the pretreatment method comprises the following steps: to the homogenized sample to be tested, 5mL of acetonitrile and 0.2g of MgSO 2 were added4Swirling for 2min, centrifuging at 4000rpm for 5min, and adding 0.09g prostate specific antigen, 0.03g nanometer bamboo charcoal and 0.3g MgSO to 3mL centrifuged supernatant to eliminate interference of navel orange matrix4Vortex for 1min, centrifuge at 4000rpm for 5min, and finally pass the centrifuged supernatant through 0.20 μm PVDF membrane.
Drawings
FIG. 1 shows UiO-66- (COOH)2、Tb3+@UiO-66-(COOH)2And TBZ @ UiO-66- (COOH)2-Tb3+The PXRD pattern of (1);
FIG. 2 shows UiO-66- (COOH)2And Tb3+@UiO-66-(COOH)2N of (A)2Adsorption-desorption isotherm diagram;
FIG. 3 shows UiO-66- (COOH)2And Tb3+@UiO-66-(COOH)2FT-IR spectrum of (1);
FIG. 4 shows UiO-66- (COOH)2And Tb3+@UiO-66-(COOH)2XPS spectra of (a);
FIG. 5 shows UiO-66- (COOH)2And Tb3+@UiO-66-(COOH)2SEM picture of (1);
FIG. 6 is Tb3+@UiO-66-(COOH)2A solid powder fluorescence spectrogram;
FIG. 7 shows UiO-66- (COOH)2A solid powder fluorescence spectrogram;
FIG. 8 is Tb3+@UiO-66-(COOH)2Change of fluorescence intensity at 544nm with timeA drawing;
FIG. 9 is pH vs. Tb3+@UiO-66-(COOH)2The effect of fluorescence intensity at 544 nm;
FIG. 10 is Tb3+@UiO-66-(COOH)2Fluorescence intensity at 544nm (a) each major component of orange and TBZ (b) each major component of orange + TBZ;
FIG. 11 is Tb3+@UiO-66-(COOH)2Time response to TBZ;
FIG. 12 is Tb3+@UiO-66-(COOH)2The change in fluorescence intensity at 544nm with TBZ concentration;
FIG. 13 is a graph of an ultraviolet absorption spectrum;
FIG. 14 is Tb3+@UiO-66-(COOH)2And TBZ @ UiO-66- (COOH)2-Tb3+(ii) XPS Spectroscopy (b) TBZ @ UiO-66- (COOH)2-Tb3+Comparison with the binding energy of N1s of TBZ itself.
Detailed Description
The present invention will be further described with reference to examples.
Example 1
Preparation of fluorescent material:
(1) preparation of MOF
0.9228g ZrCl4And 1.7208g of pyromellitic acid in 20mL of H2In O, refluxing for 24 hours at 100 ℃, centrifugally collecting after the reaction is finished, refluxing for 12 hours at 100 ℃ to remove unreacted pyromellitic acid, centrifugally collecting after the reaction is finished, soaking for 3 days by using methanol, replacing fresh methanol every day, adding acetone for solvent exchange, and finally drying for 12 hours in an oven at 60 ℃ to obtain the MOF material;
(2)Tb3+@UiO-66-(COOH)2preparation of
Weighing the UiO-66- (COOH) prepared in the step (1)20.5003g and 5.00mmol 2.2692g Tb (NO)3)3·6H2O in 50mL of H2Heating O to 60 deg.C, reacting for 24 hr while stirring, centrifuging, collecting, and purifying with H2Washing with O for three times, washing with acetone for three times, and drying at 60 deg.C for 12 hr to obtain Tb3+@UiO-66-(COOH)2A material.
Example 2
Detection of thiabendazole in navel oranges:
adding thiabendazole with different concentrations into the homogenized navel orange sample, weighing 5g of navel orange sample, adding 5mL of acetonitrile, 0.2g of MgSO4Swirling for 2min, centrifuging at 4000rpm for 5min, and adding 0.09g of prostate specific antigen, 0.03g of nano bamboo charcoal and 0.3g of MgSO (MgSO) into 3mL of centrifuged supernatant to eliminate interference of navel orange matrix4Vortex for 1min, centrifuge at 4000rpm for 5 min. Finally, the centrifuged supernatant was passed through a 0.20 μm PVDF membrane, and 1mg of Tb was added to 2mL of the filtrate3+@UiO-66-(COOH)2And carrying out ultrasonic treatment for 5min, and then carrying out fluorescence test.
Example 3
Fluorescence sensing test:
1mg of Tb3+@UiO-66-(COOH)2Dispersed in 2mL of H2Sonicating in O for 20min, adding H in 0.5mM navel orange2O，K+，Na+，Mg2+，Ca2+，NH4 +Vitamin C, fructose, glucose, citric acid, serine, glycine, lysine, alanine, carbendazim, dimethoate, malathion and thiabendazole, and the mixture was subjected to spectrum measurement.
Example 4
Characterization of the materials:
for simplicity in the drawing, UiO-66- (COOH)2I.e., MOF is abbreviated as 1, as shown in FIG. 1, PXRD pattern confirms the synthesized MOF and Tb3+The crystal structure of @1 fits well with the simulated UiO-66, indicating that our synthesized MOF has the same structure as UiO-66, and terbium functionalization does not affect its crystal structure. Preparation of 1 and Tb3+N of @12The adsorption-desorption isotherm determination experiment shows that 1 and Tb3+@1 having the same N2Adsorption-desorption isotherms, but BET of 1 from the original 388m2The/g is reduced to 129m2After the introduction of the terbium ion to 1 (FIG. 2), this is due to the steric effect of the metal cations in the pores. Quantitative analysis of 1 and Tb by ICP-MS3+Metal cation of @1The molar ratio of Zr to Tb was 5.7: 1. As shown in FIG. 3, the FT-IR spectrum of 1 was 1714cm-1A strong peak was observed due to the C ═ O stretching vibration of the non-coordinated-COOH functional group in 1, Tb after terbium functionalization3+@1，1714cm-1The peak at (a) almost completely disappeared, indicating the presence of coordination between the non-coordinated-COOH and the metal cation. This coordination was further demonstrated by XPS spectra, as shown in FIG. 4, that Tb3+ @1 exhibited a new peak at 1242.51eV compared to 1, due to the Tb 3d peak, indicating that Tb3+ was present at Tb3+ @ 1. Further, the binding energy of O1s (peak of 1s orbital electron of oxygen atom in XPS test, i.e., the energy of photoelectron measured when 1s orbital electron of oxygen atom is excited) was shifted from 531.08eV to 531.58eV at Tb3+In @1, this is because coordination of terbium ion to non-coordinated-COOH results in an increase in the binding energy of O1 s. 1 and Tb were observed by SEM3+The profile of @1 (FIG. 5), we can see 1 and Tb3+There was no significant difference in the morphology of @1, their particle size was between 20-100nm, indicating that this material was well dispersed in solution. Thermogravimetric analysis showed that 1 and Tb were at 50-200 deg.C3+@1 lost 8.58% and 9.02% of weight, respectively, due to the evaporation of the solvent molecules in the channels, and this framework only began to collapse around 400 ℃, indicating that the prepared material has good thermal stability.
Example 5
Tb3+Fluorescence and sensing properties of @ 1:
tb as shown in FIGS. 6 and 73+The @1 solid powder fluoresces brightly green, whereas 1 does not. This indicates that the free-COOH and Tb of 1 after PSM3+The ions coordinate and energy is efficiently transferred by the "antenna effect". Tb when excited with 300nm light3+The emission spectrum of @1 allows the observation of some characteristic peaks of terbium ion: 488. 544, 582 and 621nm respectively5D4→7FJ(J-6, 5,4,3) terbium transition, particularly the peak at 544nm, which is5D4→7F5The transition is caused, which is the main reason for its green fluorescence. We also explored Tb3+@1Fluorescent properties dispersed in water, and its emission pattern is similar to that of solid powder. In addition, Tb3+Fluorescence stability and pH stability of @1, FIG. 8 shows Tb3+The fluorescence intensity hardly changed when @1 was dispersed in water for 7 days, indicating that Tb3+@1 has good luminescence stability in aqueous solution. In addition, Tb3+@1 also shows good pH stability, with no significant change in fluorescence intensity between pH ranges 4-10 (figure 9). This indicates that the fluorescent probe Tb3+@1 has good application prospect in aqueous medium.
TBZ has been widely used as a pesticide for controlling crop diseases and fungicides, but may threaten public health and safety due to a large amount of residue remaining on foods. Here, Tb was investigated3+@1 potential detection of thiabendazole and its further use to monitor thiabendazole in oranges. Tb may be influenced by orange and other main components of common pesticides3+@1, thus Tb3+@1 pairs such as H2O，K+，Ca2+，Na+，Mg2+，NH4 +The luminous response of interferents such as vitamin C, fructose, glucose, citric acid, serine, glycine, lysine, alanine, carbendazim, dimethoate, malathion and the like. 1mg of Tb3+@1 was added to 2mL of each of the solutions containing the above substances (concentration: 0.5mM) with the concentration of probenazole being 0.2 mM. As shown in FIG. 10, only probenazole caused a significant decrease in fluorescence intensity among all the substances tested, vitamin C and citric acid had a slight effect, and the other 14 substances had little effect on Tb3+Fluorescence intensity of @ 1. Specificity is a key factor in the quality assurance of the sensing system, and the probe must distinguish the target molecule from other co-existing interfering molecules. Therefore, we studied Tb in the presence of other interfering molecules3+@1 specificity for probenazole detection, these interfering molecules including the major component of the orange and the usual pesticides mentioned above, all fluorescence measurements being carried out under identical conditions. The results show that the luminescence intensity is significantly reduced after the addition of probenazole, which means that probenazole is added to Tb3+Quenching of the @1 emission is not affected by the presenceThe effect of interferents. These results show that Tb3+@1 has excellent selectivity for thiabendazole. For excellent sensors, fast response is also a key criterion. We studied Tb3+@1 senses the response time to TBZ. As shown in fig. 11, Tb3+The luminescence intensity at 544nm at @1 dropped significantly and stabilized within 1 minute. The results show that Tb3+@1 may be a convenient probe for TBZ.
The detection sensitivity is Tb3+@1 as an important standard of thiabendazole sensor, Tb was studied3+The fluorescent response of @1 to different concentrations of TBZ. Homogeneous navel orange samples were spiked with different thiabendazole concentrations (0, 1, 5, 10, 20, 40, 60, 80 μ M) and fluorescence emission spectra were recorded separately. As shown in FIG. 7, the emission intensity of the probe at 544nm decreased significantly with increasing TBZ concentration, and showed good linearity in the range of 0 to 80. mu.M. Sensitivity and limit of detection (LOD) quantified from the Stern-Volmer equation:
I0/I-1＝Ksv[A]
[A]is the concentration of thiabendazole, KsvIs the quenching constant, I0And I is the luminescence intensity in the absence and presence of thiabendazole, respectively. KsvThe value was 3.5X 104M-1Linear correlation coefficient (R)2) At K, 0.995svIn the curve, this indicates Tb3+The @1 detection of thiabendazole has good quantitative analysis relation. According to IUPAC (3. sigma./slope), the detection limit was calculated to be 0.271. mu.M, which is much lower than the maximum 5ppm (about 25. mu.M) content of thiabendazole in citrus fruits. These results show that Tb3+@1 allows the quantitative detection of TBZ in oranges.
To get a thorough understanding of thiabendazole on Tb3+@1 possible quenching mechanism, Tb was studied3+@1 PXRD, shown in FIG. 1, Tb3+The sharp diffraction peak after reaction of @1 with thiabendazole did not change significantly, indicating that the MOF framework remained good in the presence of TBZ. Tb3+@1，Tb3+@1-TBZ and Tb3+The UV absorption spectrum of-TBZ Tb after reaction with thiabendazole is shown in FIG. 133+The ultraviolet absorption peak of @1 is shifted from 280nm to 298nm, and is remarkableIs thiabendazole and Tb alone3+The UV absorption peak after the reaction was also 298nm, which indicates Tb3+Tb in @13+There is an interaction with thiabendazole. Tb was further verified by XPS spectroscopy3+@1-Tb in TBZ3+Coordination interaction with thiabendazole, as shown in FIG. 14, the binding energy of N1s of thiabendazole molecule is 399.18eV, however when thiabendazole is combined with Tb3+The binding energy of N1s increased to 400.13eV after the @1 reaction, indicating that the nitrogen atom of thiabendazole and Tb3+Tb of @13+Coordination is present. Therefore, we speculate that the luminescence quenching of the probe is based on Tb3+And thiabendazole, which impairs the transition from ligand to Tb3+Energy transfer efficiency of (1).
Example 6
And (3) real sample detection:
the QuEChERS method is used as a sample pretreatment method, the performance of the probe in real samples is further tested, navel oranges (purchased from local supermarkets) containing thiabendazole with different concentrations are tested, and as shown in the table, the RSD is less than 2.73%, and the recovery rate is from 98.41% to 104.48%, which indicates that the sensor is reliable and accurate for quantitatively monitoring the thiabendazole in the real navel orange samples. The QuEChERS method can complete sample preparation in only 30 minutes, and the whole process of detecting thiabendazole is completed in 35 minutes, which is much faster than the traditional method for detecting thiabendazole in orange samples.
Claims (1)
- The application of Tb-MOF fluorescent material in rapid detection of thiabendazole in navel orange is characterized in that: the Tb-MOF fluorescent material consists of UiO-66- (COOH)2And Tb (NO)3)3·6H2O, the Tb-MOF fluorescent material is prepared by the following steps:(1) preparation of MOFReacting ZrCl4And pyromellitic acid in H2Performing first reflux at 100 deg.C in O, centrifuging and collecting after reaction, performing second reflux at 100 deg.C to remove unreacted pyromellitic acid, centrifuging and collecting precipitate, soaking in methanol for 3 days, replacing fresh methanol every day,adding acetone for solvent exchange, and drying in an oven at 60 deg.C for 12 hr to obtain MOF material, which is UiO-66- (COOH)2；(2) Preparation of Tb-MOF fluorescent materialMixing the MOF material prepared in step (1) with Tb (NO)3)3·6H2O is dispersed in H2Heating O to 60 deg.C, stirring for reaction, centrifuging to collect precipitate, and adding H2Washing with O for three times, washing with acetone for three times, and drying at 60 ℃ for 12 hours to obtain the Tb-MOF fluorescent material;in the step (1), ZrCl4The dosage of the compound is 0.9228g, and the dosage of the pyromellitic acid is 1.7208 g;the time of the first reflux in the step (1) is 24 hours, and the time of the second reflux is 12 hours;in the step (2), the dosage of the MOF is 0.5003g, Tb (NO)3)3·6H2The dosage of O is 2.2692 g;the detection method comprises the following steps: and adding the Tb-MOF fluorescent material into the pretreated sample to be tested, carrying out ultrasonic treatment for 5min, and then carrying out fluorescence test.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102365369A (en) * | 2009-02-27 | 2012-02-29 | 先正达参股股份有限公司 | Detection method |
| CN103926223A (en) * | 2013-01-14 | 2014-07-16 | 宁波大学 | Fluorescent probe for selective recognition of fluorine ion |
| CN105300936A (en) * | 2015-09-16 | 2016-02-03 | 北京师范大学 | Determination of yeast RNA (Ribonucleic Acid) by photoluminescence of ruthenium-based metal complex |
| CN108593609A (en) * | 2018-03-27 | 2018-09-28 | 南昌大学 | A kind of method of highly sensitive highly selective fluoroscopic examination magnesium ion |
| CN110938215A (en) * | 2019-12-26 | 2020-03-31 | 烟台大学 | Eu3+-MOF material preparation method and application thereof |
| CN111398232A (en) * | 2020-04-07 | 2020-07-10 | 浙江大学 | Fluorescence detection method for concentration of ions to be detected in transformer oil |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180311347A1 (en) * | 2017-04-25 | 2018-11-01 | University Of Southern California | Polymorphisms in cachexia predict clinical outcomes of colorectal cancer patients receiving irinotecan and bevacizumab |
-
2020
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102365369A (en) * | 2009-02-27 | 2012-02-29 | 先正达参股股份有限公司 | Detection method |
| CN103926223A (en) * | 2013-01-14 | 2014-07-16 | 宁波大学 | Fluorescent probe for selective recognition of fluorine ion |
| CN105300936A (en) * | 2015-09-16 | 2016-02-03 | 北京师范大学 | Determination of yeast RNA (Ribonucleic Acid) by photoluminescence of ruthenium-based metal complex |
| CN108593609A (en) * | 2018-03-27 | 2018-09-28 | 南昌大学 | A kind of method of highly sensitive highly selective fluoroscopic examination magnesium ion |
| CN110938215A (en) * | 2019-12-26 | 2020-03-31 | 烟台大学 | Eu3+-MOF material preparation method and application thereof |
| CN111398232A (en) * | 2020-04-07 | 2020-07-10 | 浙江大学 | Fluorescence detection method for concentration of ions to be detected in transformer oil |
Non-Patent Citations (4)
| Title |
|---|
| Highly selective detection of Cu2+ in aqueous media based on Tb3+ functionalized metal-organic framework;Xiong-Xin Peng et al.，;《Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy》;20200618;第240卷;第1-8页 * |
| Surface-enhanced Raman spectroscopy coupled with gold nanoparticles for rapid detection of phosmet and thiabendazole residues in apples;Hairui Luo et al.，;《Food Control》;20160404;第68卷;第229-235页 * |
| Xiong-Xin Peng et al.，.Highly selective detection of Cu2+ in aqueous media based on Tb3+ functionalized metal-organic framework.《Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy》.2020,第240卷 * |
| 荧光增强法测定噻菌灵新体系;毛树禄等;《光谱实验室》;20130331;第30卷(第2期);第579-583页 * |
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