CN114805826A - Eu (Eu) 3+ Functionalized MOF fluorescent probe, preparation method thereof and application of functionalized MOF fluorescent probe in detection of tetracycline drugs - Google Patents
Eu (Eu) 3+ Functionalized MOF fluorescent probe, preparation method thereof and application of functionalized MOF fluorescent probe in detection of tetracycline drugs Download PDFInfo
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Abstract
The invention discloses Eu 3+ A functional MOF fluorescent probe, a preparation method thereof and application of the functional MOF fluorescent probe in detecting tetracycline drugs, wherein the Eu is 3+ Functional MOF fluorescent probe to enable Eu to be detected 3+ Introduction of UiO-66- (COOH) 2 Prepared from/p-CBA, the Eu 3+ The functionalized MOF fluorescent probe has high selectivity and sensitivity to tetracycline drugs. Eu prepared by the invention 3+ The functional MOF fluorescent probe shows high selectivity and high sensitivity to 6 typical tetracycline antibiotics, wherein the 6 typical tetracycline antibiotics are oxytetracycline, chlortetracycline, methylenetetracycline, minocycline, tetracycline and doxycycline, so that the Eu3+ functional MOF fluorescent probe can be used for detection of tetracycline drugs, particularly for detection of pig wastewater and pig kidneyDoxycycline.
Description
Technical Field
The invention belongs to the technical field of fluorescent probes, and particularly relates to a Eu3+ functionalized MOF fluorescent probe, a preparation method thereof and application of the Eu3+ functionalized MOF fluorescent probe in detection of tetracycline drugs.
Background
Tetracyclines (TCs) are broad-spectrum antibiotics used primarily for the treatment of diseases associated with humans and farm animals. The consumption of tetracycline is up to 5000 metric tons every year, but the natural degradation of tetracycline in the environment is difficult and long, so that the excessive use of tetracycline easily causes the accumulation of tetracycline in the environment, the residue of tetracycline in the environment can cause the drug resistance of bacteria, and the genetic variation generates drug-resistant bacteria. Abuse of tetracyclines in farming in animal husbandry leads to increased antibiotic residues in animal by-products such as meat, eggs, milk, etc. Consumption of these antibiotic-containing residues in large quantities can result in excessive antibiotic levels in humans, which further causes tetracycline teeth, allergic reactions, gastrointestinal disturbances and liver poisoning, while the development of drug-resistant bacteria can further lead to more serious diseases. Therefore, monitoring the tetracycline drugs in the environment and culture byproducts is of great significance.
Up to now, various technologies such as Capillary Electrophoresis (CE), liquid chromatography-tandem mass spectrometry (LC-MS/MS), electrochemical sensors, biosensors, and the like have been used for monitoring tetracycline drugs, and all have high sensitivity and high selectivity to the tetracycline drugs. However, these methods are relatively cumbersome and complex to operate, and require professional personnel to assist in performing the test, so it is necessary to develop a simple and rapid detection method.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a Eu3+ functionalized MOF fluorescent probe, a preparation method thereof and application of the probe in detection of tetracycline drugs, and the technical scheme is as follows:
eu (Eu) 3+ A functionalized MOF fluorescent probe, reacting Eu 3+ Introduction of UiO-66- (COOH) 2 Prepared from/p-CBA.
Therefore, the invention also provides Eu 3+ The application of the functionalized MOF fluorescent probe in the field of tetracycline drug detection, preferably the application of detecting doxycycline in pig wastewater and pig kidney. Through research, the Eu 3+ The functionalized MOF fluorescent probe shows high selectivity and high sensitivity to 6 typical tetracycline antibiotics, and the 6 typical tetracycline antibiotics are oxytetracyclineAureomycin, methylenetetracycline, minocycline, tetracycline and doxycycline, the Eu 3+ The detection limits of the functionalized MOF fluorescent probe for oxytetracycline, chlortetracycline, methylenetetracycline, minocycline, tetracycline, and doxycycline were 0.118. mu.M, 0.228. mu.M, 0.102. mu.M, 0.138. mu.M, 0.206. mu.M, and 0.078. mu.M, respectively.
The invention also provides Eu 3+ The preparation method of the functionalized MOF fluorescent probe comprises the following steps: (1) preparation UiO-66- (COOH) 2 p-CBA: heating 30mL of an aqueous solution containing 1.38g of pyromellitic acid, 204mg of p-CBA and 0.92g of zirconium tetrachloride at 110 ℃ under reflux for 24 hours to obtain a suspension, centrifuging the suspension, removing the supernatant to obtain a white gel-like solid at the bottom, washing the gel-like solid with ultrapure water, and dispersing the gel-like solid in 40mLH 2 Refluxing in O at 110 deg.C for 16 hr, centrifuging to obtain white gel solid, washing with water and ethanol, and vacuum drying at 80 deg.C to obtain UiO-66- (COOH) 2 /p-CBA；
(2) Preparation of EuUCBA: 0.30g of UiO-66- (COOH) 2 p-CBA and 1.10g EuCl 3 -6H 2 O was mixed in 30ml of water, reacted at 80 ℃ for 24 hours, and centrifuged to obtain a white solid, which was washed with water and ethanol, respectively, and then vacuum-dried at 80 ℃ to obtain EuUCBA.
Preferably, the suspension of step (1) is centrifuged at 8000rpm/min for 5 minutes.
The white gel-like solid in the step (1) is washed three times with ultrapure water, and the white gel-like solid is washed three times with water and ethanol, respectively.
The white solid in step (2) was washed three times with water and ethanol, respectively.
In step (2), the mixture was dried under vacuum at 80 ℃ for 8 hours.
The invention has the beneficial effects that: eu prepared by the invention 3+ The functionalized MOF fluorescent probe shows high selectivity and high sensitivity to 6 typical tetracycline antibiotics, wherein the 6 typical tetracycline antibiotics are oxytetracycline, chlortetracycline, methylenetetracycline, minocycline, tetracycline and doxycycline, and the Eu is 3+ The functional MOF fluorescent probe is used for oxytetracycline, chlortetracycline, methylenetetracycline,The detection limits for minocycline, tetracycline and doxycycline were 0.118. mu.M, 0.228. mu.M, 0.102. mu.M, 0.138. mu.M, 0.206. mu.M and 0.078. mu.M, respectively. Therefore, the Eu3+ functionalized MOF fluorescent probe can be used for detecting tetracycline drugs, and is particularly applied to detecting doxycycline in pig wastewater and pig kidneys.
Drawings
FIG. 1 shows Eu according to the present invention 3+ A scheme for synthesis of functionalized MOF fluorescent probes (EuUCBA) and sensing TCs;
FIG. 2(a) shows the present invention UiO-66- (COOH) 2 PXRD patterns of the crystal structures of/p-CBA and EuUCBA; FIG. 2(b) shows UiO-66- (COOH) 2 FT-IR spectra of/p-CBA and EuUCBA; FIG. 2(c) shows UiO-66- (COOH) 2 XPS spectra of/p-CBA and EuUCBA; FIG. 2(d) shows UiO-66- (COOH) 2 O1s binding energy of/p-CBA and EuUCBA;
FIG. 3 shows the present invention UiO-66- (COOH) 2 N of/p-CBA and EuUCBA 2 Adsorption-desorption isotherm curves;
FIG. 4 shows the present invention UiO-66- (COOH) 2 Thermogravimetric curves of/p-CBA and EuUCBA;
FIG. 5 shows fluorescence spectra of EuUCBA of the present invention in solid state;
FIG. 6 shows fluorescence spectra of EuUCBA of the present invention under aqueous suspension;
FIG. 7(a) is a fluorescence spectrum of EuUCBA according to the present invention immersed in water for different days; FIG. 7(b) is the fluorescence intensity of EuUCBA at 613nm at different pH values;
FIG. 8(a) is a graph showing the fluorescence intensity at 613nm of EuUCBA of the present invention after addition of TCs and other analytes; FIG. 8(b) is a graph comparing the fluorescence intensity at 613nm of EuUCBA with and without DOXY when other analytes are added;
FIG. 9 shows EuUCBA of the present invention with varying concentrations of (a) DOXY; (c) OTC; and (e) fluorescence spectra of CTCs. The fluorescence intensity of EuUCBA at 613nm with (b) DOXY; (d) OTC; and (f) a linear relationship between the concentration of CTCs;
FIG. 10 is a fluorescence emission spectrum of EuUCBA of the present invention with different concentrations of (a) MTC, (c) MOC, and (e) TC; a linear relationship between the fluorescence intensity of EuUCBA at 613nm and the concentrations of (b) MTC, (d) MOC, and (f) TC;
FIG. 11 is a time kinetics of the addition of doxycycline to EuUCBA of the present invention;
FIG. 12 shows the temporal kinetics of probe Eu UCBA after addition of (a) OTC, (b) CTC, (c) MTC, (d) MOC and (e) TC;
FIG. 13 is a PXRD pattern of the EuUCBA reacted with DOXY of the present invention;
FIG. 14 shows DOXY EuCl of the present invention 3 And UiO-66- (COOH) 2 UV spectrum of/p-CBA.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments and the accompanying drawings to fully understand the objects, aspects and effects of the present invention.
The chemicals and instruments used in the present invention:
chemical products:
zirconium tetrachloride (ZrCl) 4 98%) was obtained from jiding chemical (china); 4-formylbenzoic acid (p-CBA, 98%) was purchased from Michelin reagent; pyronic acid and veterinary drugs are commercially available from alatin reagent (china).
The instrument comprises the following steps:
x-ray powder diffraction (XRD) patterns were obtained by a D8 Advance diffractometer with Cu ka radiation (λ 0.15406 nm);
FT-IR spectra were obtained from Perkin Elmer spectrum-II;
x-ray photoelectron spectroscopy (XPS) was performed on Thermo Fisher Scientific Escalab 250Xi using monochromatic Al K α (h v 1486.6 eV);
thermogravimetric analysis (TGA) was performed on a Perkinelmer TGA4000 with a heating rate of 10 ℃/min under nitrogen atmosphere;
the concentration of metal ions was measured by ICP-MS of agilent technologies;
on a Micrometrics TriStar II Plus (Micromeritics, U.S.A.), N was used 2 Adsorption-desorption isotherm curves BET surface areas were measured at 77K;
fluorescence spectra were obtained with an Edinburgh FS5 fluorometer;
UV-vis absorption spectra were obtained from Perkinelmer Lambda 750 s.
Example 1
Preparation of Eu 3+ The synthesis route of the functionalized MOF fluorescent probe is shown in figure 1:
(1) preparation UiO-66- (COOH) 2 p-CBA: heating 30mL of an aqueous solution containing 1.38g of pyromellitic acid, 204mg of p-CBA and 0.92g of zirconium tetrachloride at 110 ℃ for refluxing for 24 hours to obtain a suspension, centrifuging the suspension at 8000rpm/min for 5 minutes, discarding the supernatant to obtain a white gel-like solid at the bottom, washing the gel-like solid three times with ultrapure water, and dispersing the gel-like solid in 40mLH 2 Refluxing in O at 110 deg.C for 16 hr, centrifuging to obtain white gel solid, washing with water and ethanol for three times, and vacuum drying at 80 deg.C to obtain UiO-66- (COOH) 2 /p-CBA；
(2) Preparation of EuUCBA: 0.30g of UiO-66- (COOH) 2 p-CBA and 1.10g EuCl 3 -6H 2 O was mixed in 30ml of water, reacted at 80 ℃ for 24 hours, and centrifuged to obtain a white solid, which was washed with water and ethanol, respectively, and vacuum-dried at 80 ℃ for 8 hours to obtain EuUCBA.
Example 2
Determination of Eu 3+ Characterization of functionalized MOF fluorescent probes:
UiO-66-(COOH) 2 powder X-ray diffraction (PXRD) of the crystalline structures of/p-CBA and EuUCBA As shown in FIG. 2(a), it can be seen that PXRD pattern of the synthesized MOFs is well matched with the simulated pattern of UiO-66, indicating that the synthesized MOFs and UiO-66 are of homogeneous structure and UiO-66- (COOH) 2 Incorporation of medium p-CBA and Eu 3+ Does not affect its structural framework.
FT-IR spectrum of the synthesized MOFs was shown in FIG. 2(b), and UiO-66- (COOH) was observed 2 p-CBA at 1720cm -1 The peak at (A) is due to the vibration of the free-COOH group, in contrast to 1712cm in EuUCBA -1 The peak of (A) is rather weak, which means that there is a free carboxylic acid group with Eu 3+ And (4) coordination.
XPS spectra of the synthesized MOFs are shown in FIG. 2(c), and further confirm that Eu 3+ and-COO - Coordinate with each otherAnd (4) acting. UiO-66- (COOH) 2 The O1s binding energies of/p-CBA and EuUCBA are shown in FIG. 2(d), and from FIGS. 2(c) and (d), the binding energy of Eu 3d was observed at 1241.65eV, indicating the presence of Eu in the probe 3+ . Furthermore, in UiO-66- (COOH) 2 In p-CBA, the binding energy of O1s is 524.23eV, whereas in EuUCBA the binding energy is shifted to 525.03eV, indicating-COO - And Eu 3+ There is a coordination interaction between them.
To confirm Eu in the probe 3+ Existence of Zr calculated by ICP-MS analysis 4+ And Eu 3+ The molar ratio in probe EuUCBA was 6.58:1, indicating that Eu is present 3+ In UiO-66- (COOH) 2 Post-modification was successfully performed on/p-CBA.
BET surface area of the synthesized MOFs from N 2 The adsorption-desorption isotherm is shown in FIG. 3, UiO-66- (COOH) 2 BET surface areas of 349.12m for/p-CBA and EuUCBA, respectively 2 G and 230.82m 2 G, it can be seen that the reduction of the BET surface indicates Eu 3+ The ions successfully enter UiO-66- (COOH) 2 In the pores of the/p-CBA.
UiO-66-(COOH) 2 The thermogravimetric curves of/p-CBA and EuUCBA are shown in FIG. 4, and it can be seen that UiO-66- (COOH) 2 The weight loss rates of/p-CBA and EuUCBA were 26.42% and 28.99% respectively in the range of 40-400 deg.C, which is attributed to loss of solvent molecules, and the MOF framework starts to decompose around 400 deg.C, showing its thermal stability.
Example 3
Determination of Eu 3+ Luminescence properties of the functionalized MOF fluorescent probes:
the fluorescence spectrum of EuUCBA in the solid state is shown in FIG. 5, and the fluorescence spectrum of EuUCBA in aqueous suspension is shown in FIG. 6. It can be seen that the probe showed Eu in both solid state and in aqueous suspension 3+ Bright red light of the ion, which means energy from the ligand to Eu 3+ Efficient transfer of ions. Although the excitation spectrum in the aqueous suspension is different from that in the solid state, the emission spectrum of EuUCBA shows Eu alone in both the solid state and the aqueous state 3+ A transmission band. Eu was observed at 579, 592, 650 and 699nm 3+ Due to a characteristic emission band of 5 D 0 → 7 F J (J ═ 1-5). The main peak is at 613nm, and emits intense bright red light under ultraviolet irradiation.
In addition, the luminescence of EuUCBA probe was very stable. The fluorescence spectra of EuUCBA after immersion in water for various days are shown in FIG. 7(a), and it can be seen that the emission intensity at 613nm shows negligible change after 1 week of storage of the EuUCBA probe in water. The fluorescence intensity of EuUCBA at 613nm at various pH values is shown in FIG. 7(b), and it can be seen that the EuUCBA probe is stable in the pH range of 4-11 and suitable for detecting TCs.
To investigate the response of EuUCBA probes to different antibiotics, 36 different veterinary drugs (0.1M, 6 μ L) were added to an aqueous suspension of EuUCBA (2mL, 1mg) and the respective profiles were scanned on a fluorimeter. The 36 veterinary drugs include Tobramycin (TOB), gentamicin sulfate (CN), kanamycin sulfate (K), Andrographolide (AN), Abamectin (AVM), Apramycin (APR), D-mannose (D-Man), Aminopyrine (AM), vancomycin hydrochloride (VA), Spectinomycin (SH), Amantadine Hydrochloride (AH), amproline hydrochloride (AMP), Cephalosporin (CL), Chloral Hydrate (CH), bisphenol a (bpa), albuterol (SAL), neomycin sulfate (N), streptomycin sulfate (S), amikacin sulfate (AK), lincomycin (MY), Ribavirin (RBV), Sulfathiazole (STH), Sulfadiazine (SD), Baclofen (BAC), erythromycin (E), florfenicol (FFC), Dexamethasone (DEX), Ivermectin (IVM), Isoniazid (INH), Mequindox (MEQ), Methacycline (MTC), Minocycline (MOC), Tetracycline (TC), Oxytetracycline (OTC), chlortetracycline (CTC), and Doxycycline (DOXY).
The fluorescence intensity of the EuUCBA probe at 613nm added with 36 different veterinary drugs is shown in figure 8(a), and only tetracyclines including DOXY, TC, CTC, MOC, MTC and OTC can greatly quench the fluorescence of the probe at 613 nm; in contrast, the fluorescence intensity decreased slightly after addition of VA, BPA, RBV, STH, SD, BAC, IVM and INH; the influence of all other veterinary drugs on the fluorescence intensity of the probe at 613nm can be ignored; it can be seen that the high selectivity of EuUCBA probe towards TCs, DOXY showed the most efficient fluorescence quenching at 613nm in TCs.
Fast response and interference immunity are important factors for practical sensing applications. The effect of other veterinary drugs on DOXY induction was studied. mu.L of 0.1M DOXY was added to 2mL of probe (1mg) containing other veterinary drugs (0.3mM), and the fluorescence intensity at 613nm was recorded, and the fluorescence intensity at 613nm after addition of other analytes in the presence or absence of DOXY in EuUCBA was compared as shown in FIG. 8(b), and the luminescence intensity at 613nm was significantly reduced in the presence of DOXY, indicating that the probe had good anti-interference effects on the detection of DOXY.
The luminescence titration experiment was carried out by gradually dropping TCs into an aqueous suspension of probe EuUCBA, as shown in FIGS. 9 and 10, in the range of 0 to 100. mu.M for DOXY, OTC and MOC, 0 to 80. mu.M for CTC and MTC, and 0 to 50. mu.M for TC, the luminescence intensity at 613nm gradually decreased with the addition of each TC. The quenching effect was determined quantitatively by the Stern-Volmer (S-V) equation:
I 0 /I＝K sv ·C TCs +1
wherein K sv Is the quenching constant (M) -1 )；I 0 And I is the fluorescence intensity in the absence and presence of TCs, C TCs Is the concentration of the tetracycline drug solution. The limit of detection (LOD) is determined as 3 sigma/s, K sv 、R 2 And LOD values are shown in Table 1.
TABLE 1K for different tetracyclines sv ,R 2 And LOD value
The time dynamics of EuUCBA after adding DOXY is shown in figure 11, in addition, the time dynamics of probe EuUCBA after adding OTC, CTC, MTC, MOC and TC is shown in figures 12(a), 12(b), 12(c), 12(d) and 12(e), the obvious reduction and the plateau of 613nm fluorescence intensity can be seen in 30 seconds, the rapid reaction shows that the probe is suitable for the real-time detection of DOXY, and because the probe shows the prominent sensitivity to DOXY in TCs, the anti-interference performance is strong, only the DOXY is detected in the practical application.
PXRD patterns and UV-visible spectra such asAs shown in fig. 13, it can be seen that the main PXRD peak of DOXY @ EuUCBA is very weak but still consistent with the original EuUCBA, indicating that the main framework is retained after detection of DOXY. UiO-66- (COOH) 2 p-CBA, DOXY and EuCl 3 The UV-visible absorption spectrum of (A) is shown in FIG. 14, and it can be seen that DOXY and UiO-66- (COOH) 2 The absorption bands of the/p-CBA overlap. Thus, the possible quenching mechanism of EuUCBA emission by DOXY is that energy is transferred from UiO-66- (COOH) with the presence of DOXY 2 Transfer of p-CBA to DOXY molecule reduces UiO-66- (COOH) 2 p-CBA to Eu 3+ Further leading to fluorescence quenching.
Example 4
Eu 3+ Detection of the functionalized MOF fluorescent probe on DOXY in the pig kidney and pig wastewater samples:
EuUCBA quantitatively detects DOXY in pig kidneys and pig wastewater samples, and as shown in Table 2, the calculated recovery rate is 98.41% -107.39% in pig wastewater and 90.96% -110.08% in pig kidneys.
TABLE 2EuUCBA assay for doxycycline in porcine kidney extract and porcine wastewater samples
In conclusion, the novel Eu-MOF fluorescent probe EuUCBA has good fluorescence characteristics and is quite stable in an aqueous solution with the pH value of 4-11. EuUCBA can specifically identify TCs from 36 commonly used veterinary drugs and cause significant fluorescence changes, even in the presence of these commonly used veterinary drugs, with little interference with the ability of EuUCBA to detect TCs. The detection sensitivity of the fluorescent probe EuUCBA to TCs is high (the detection limit is in the range of 0.078-0.228 mu M). In addition, the probe EuUCBA can be applied to the detection of the DOXY content in the pig wastewater and the actual sample of the pig kidney, and the good recovery rate and the lower RSD value show that the probe EuUCBA is reliable in practical application.
While the present invention has been described in considerable detail and with particular reference to a few illustrative embodiments thereof, it is not intended to be limited to any such details or embodiments or any particular embodiments, but it is to be construed as effectively covering the intended scope of the invention by providing a broad, potential interpretation of such claims in view of the prior art with reference to the appended claims. Furthermore, the foregoing describes the invention in terms of embodiments foreseen by the inventor for which an enabling description was available, notwithstanding that insubstantial modifications of the invention, not presently foreseen, may nonetheless represent equivalent modifications thereto.
Claims (8)
1. Eu (Eu) 3+ The functional MOF fluorescent probe is characterized in that Eu is added 3+ Introduction of UiO-66- (COOH) 2 Prepared from/p-CBA.
2. Eu according to claim 1 3+ The application of the functionalized MOF fluorescent probe in the field of tetracycline drug detection.
3. Use according to claim 2, wherein said Eu is 3+ The application of the functionalized MOF fluorescent probe in detecting doxycycline in pig wastewater and pig kidney.
4. Eu (Eu) 3+ The preparation method of the functionalized MOF fluorescent probe is characterized by comprising the following steps:
(1) preparation UiO-66- (COOH) 2 p-CBA: heating 30mL of an aqueous solution containing 1.38g of pyromellitic acid, 204mg of p-CBA and 0.92g of zirconium tetrachloride at 110 ℃ under reflux for 24 hours to obtain a suspension, centrifuging the suspension, removing the supernatant to obtain a white gel-like solid at the bottom, washing the gel-like solid with ultrapure water, and dispersing the gel-like solid in 40mLH 2 Refluxing in O at 110 deg.C for 16 hr, centrifuging to obtain white gel solid, washing with water and ethanol, and vacuum drying at 80 deg.C to obtain UiO-66- (COOH) 2 /p-CBA；
(2) Preparation of EuUCBA: 0.30g of UiO-66- (COOH) 2 p-CBA and 1.10g EuCl 3 -6H 2 O was mixed in 30ml of water, reacted at 80 ℃ for 24 hours, and centrifuged to obtain a white solid, which was washed with water and ethanol, respectively, and then vacuum-dried at 80 ℃ to obtain EuUCBA.
5. Eu according to claim 4 3+ The preparation method of the functionalized MOF fluorescent probe is characterized in that the suspension in the step (1) is centrifuged at 8000rpm/min for 5 minutes.
6. Eu according to claim 4 3+ The preparation method of the functionalized MOF fluorescent probe is characterized in that the white gelatinous solid in the step (1) is washed three times by using ultrapure water, and the white gelatinous solid is washed three times by using water and ethanol respectively.
7. Eu according to claim 4 3+ The preparation method of the functionalized MOF fluorescent probe is characterized in that the white solid in the step (2) is washed three times by water and ethanol respectively.
8. Eu according to claim 4 3+ The preparation method of the functionalized MOF fluorescent probe is characterized in that the functionalized MOF fluorescent probe is dried in vacuum at 80 ℃ for 8 hours in the step (2).
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| CN118225746A (en) * | 2024-03-18 | 2024-06-21 | 江西科技师范大学 | Method for rapidly, simply, conveniently and highly sensitively quantitatively detecting tetracycline in water sample |
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