CN114672302A - Preparation and application of near-infrared MOF fluorescent probe based on silarhodamine - Google Patents
Preparation and application of near-infrared MOF fluorescent probe based on silarhodamine Download PDFInfo
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Abstract
The invention relates to preparation and application of a near-infrared MOF fluorescent probe for Adenosine Triphosphate (ATP) detection based on silicorhodamine, wherein the fluorescent probe is structurally composed of a nanoscale metal organic framework (ZIF-90) and a near-infrared fluorophore based on the silicorhodamine, and the near-infrared fluorophore is wrapped in the nanometer metal organic framework. The invention provides a preparation method for synthesizing a fluorescent probe by using 3-Br-N, N-dimethylaniline, N-butyllithium, dichlorodimethylsilane, 2-formylbenzoic acid, imidazole-2-formaldehyde, zinc acetate dihydrate and the like as raw materials; the fluorescent probe is an adenosine triphosphate near infrared MOF fluorescent probe based on silarhodamine; firstly, the synthesis method of the fluorescent probe is simple, and the fluorescence enhancement of 8.5 times can be generated on ATP; secondly, the fluorescent probe has relatively ideal selectivity for ATP and is not interfered by other nucleotides and common ions in organisms; thirdly, the fluorescent probe has rapid action with ATP and response time within 500 s; in addition, the near infrared emission wavelength of the fluorescent probe is longer, and the fluorescent probe can be used for detecting the ATP content in living cells.
Description
Technical Field
The invention belongs to the technical field of fluorescent probes, and particularly relates to preparation and application of an adenosine triphosphate near-infrared MOF fluorescent probe based on silarhodamine.
Background
Adenosine Triphosphate (ATP) is produced mainly in mitochondria and is the source of energy required for vital activities in organisms (Schulz G E.binding of nucleotides by proteins [ J ]. curr. Opin. in struc. biol.,1992,2, 61-67; Roberts J.control of the supporting line [ J ]. Science,1997,278, 2073-. It is involved in various physiological processes such as protein synthesis, energy transfer, cellular respiration, enzymatic catalysis, signal transduction (SzewcyK A, Pikula S.Adenosine 5' -triphosphatate: an intercellular metabolic messenger [ J ]. Biochim. Biophys. acta Rev. Cancer,1998,1365, 333. sup. 353. Zhou Y, Tozzi F, Chen J, Fan F, Xia L, Wang J, Gao G, Zhang A, Xia X, Brasher H, Widget W, Ellis L M, Zhang W.Intracular ATP. vascular peptide derivative 2011 of chemistidianin cell cells [ J ]. Cancer, Res, 72.). Further, ATP concentration in cells is closely related to many diseases such as ischemic injury, platelet aggregation, inflammation and malignant tumor, etc., and thus ATP can be studied as a marker of some diseases (Morcia G, Sarti A C, Marchi S, Missiroli S, Falzoni S, Raffaghello L, Pistoia V, Giorgi C, Di Virgilio F, Pitton P.use of luminescence probes to ATP in living cells and animals [ J ]. Nature Protoc, 2017,12: 1542; rham E H, Okunieff P, Scala S, Vos P, Oosterved M J S, Chenn A Y, Shrivastav B, Guidic G. cytotoxic fibrosis and protein complex [ 1325 J. ] Science, 275, J.6, J.1997). It is necessary to develop a simple and effective ATP detection method for further understanding and studying ATP-related physiological and pathological processes.
In recent years, various methods have been developed for ATP detection, such as colorimetry, chemiluminescence, electrochemical analysis, fluorescence detection, and the like (Li S, ZHao X, Yu X, Wan Y, Yin M, Zhang W, Cao B, Wang H.Fe)3O4 nanozymes with aptamer-tuned catalysis for selective colorimetric analysis of ATP in blood[J].Anal.Chem.,2019,91,14737-14742；Yao W,Wang L,Wang H,Zhang X,Li L.An aptamer-based electrochemiluminescent biosensor for ATP detection[J].Biosens.Bioelectron.,2009,24,3269-3274；Xie H,Chai Y,Yuan Y,Yuan R.Highly effective molecule converting strategy based on enzyme-free dual recycling amplification for ultrasensitive electrochemical detection of ATP[J]Chem. Commun.,2017,53, 8368-) -. Compared with other detection methods, the fluorescence method has the advantages of high sensitivity, good selectivity, fast response, strong imaging resolution and the like, and is widely used for detection and analysis of organisms (Zhou Y, Xu Z, Yoon J. fluorescence and colorimetric cheminsensors for detection of nucleotides, FAD and NADH: high-height research reduce 2004-]Chem.soc.rev.,2011,40, 2222-. However, most of the currently reported ATP fluorescent probes have the disadvantages of insufficient hydrophilicity, poor biocompatibility, complex synthesis, and the like, and thus the requirements of biological living body imaging are difficult to achieve. Therefore, it is necessary to design a fluorescent probe capable of detecting near infrared emission of ATP levels in vivo.
Zeolitic Imidazolate Frameworks (ZIFs), a subclass of metal-organic frameworks (MOFs), are formed by self-assembly of metal ions and imidazole linkers. Because of its advantages of adjustable porosity, controllable structure, high loading rate, good biocompatibility, easy synthesis and functionalization, etc., it is widely studied and applied in the fields of catalysis, gas storage and separation, drug delivery, biological imaging and sensing, etc. (Khan N A, Hasan Z, Jhung S H.beyond and patent metal-organic frames: Preparation and application of nanostructed, nanosized, and organic MOFs [ J ] associated with organic frame.Rev., 2018,376, 20-45; Xu C, Fang R, Luque R, Chen L, Li Y.functional-organic frame for organic application [ J ] associated with organic frame.Rev., 2018, 201268, 292; Jiang L, wai L, J.associated with organic frame.Rev., 2018, J ] associated with organic frame.Rev., 2018, 19, J.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.D., 9, 268, D.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.A. D., X.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.A. 9, D. 9, D.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.A. Ser. 9, D. 9, D.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.D.S.S.D.D.S.S.S.S.S.D.S.S.D.D.S.D.D.S.D.D.D.S.D.D.D.D.S.A. Ser. No. D.D.D.D.S.D.D.D.D.D.D.D.A. D.S.D.D.D.D.D.D.D.D.S.D.A. D.D.D.D.S.D.D.S.A. D.D.A. D.D.S.D.D.A. D.S.S.S.S.S.S.S.S.S.S.D.D.D.D.D.S.D.D.S.D.D.D.S.D.A. D.A.D.A. D.A.A.A.A.A.D.D.D.D.D.D.D.D.D.D.A.A. D.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A. D.A.A.A.A.A.A.A.A.A.A.A.A. In recent years, a large number of MOF materials have been reported for drug, protein and small molecule dye entrapment. However, there are few reports of using this to detect ATP in vivo. Therefore, the combination of the nano material and the near-infrared fluorescent dye has important significance in developing a MOFs-based near-infrared fluorescent probe for detecting ATP in a living body.
Disclosure of Invention
In light of the requirements, the present inventors have conducted intensive studies to provide an adenosine triphosphate near-infrared nano fluorescent probe based on a metal organic framework (ZIF-90) after a great deal of creative work.
The invention has the technical scheme that the near-infrared MOF fluorescent probe based on the silicorhodamine is structurally formed by self-assembling a metal organic framework (ZIF-90) and a silicorhodamine near-infrared fluorescent dye (SiB).
A preparation method of a near-infrared MOF fluorescent probe based on silarhodamine. The method comprises the following steps:
1) the preparation method of the silicon rhodamine near infrared fluorescent dye (SiB) comprises the following steps: at 0 ℃ N2Adding 1.5-2.5 equivalents of 3-Br-N, N-dimethylaniline into a 200mL double-neck round-bottom flask containing 60mL of diethyl ether under protection, adding 1.5-2.5 equivalents of N-butyllithium, and reacting for 1.5-2.5 h. Dissolving 0.5-1.5 equivalent of dichlorodimethylsilane into 10mL of diethyl ether, slowly adding the mixture into the reaction, reacting overnight after the reactants gradually return to room temperature, and adding 50mL of water to quench the reaction. The reaction mixture was extracted with ether, washed with brine, and dried over anhydrous sodium sulfate. The crude product was purified by silica gel column chromatography using petroleum ether/ethyl acetate (80:1) as eluent, and the solvent was distilled off under reduced pressure to give a pale yellow oily intermediate (yield 75%). Adding 8-12 equivalents of intermediate product, 40-60 equivalents of 2-formylbenzoic acid and 0.5-1.5 equivalents of copper bromide into a 15mL sealed tube, and stirring to react for 5 hours at 140 ℃; after cooling to room temperature, the reaction mixture was dissolved in dichloromethane, extracted with 2M NaOH solution, and the organic layer was washed with brine and dried over anhydrous sodium sulfate. The crude product was purified by silica gel column chromatography using petroleum ether, ethyl acetate and triethylamine (50:1:1) as eluent, and the solvent was distilled off under reduced pressure to obtain colorless needle-like crystals (yield 45%).
2) A preparation method of a near-infrared MOF fluorescent probe (ZIF-90@ SiB) based on silicorhodamine comprises the following steps: adding 2mL of N, N-dimethylformamide into 90-110 equivalents of zinc acetate dihydrate at room temperature to completely dissolve the zinc acetate dihydrate, simultaneously completely dissolving 180-220 equivalents of imidazole-2-formaldehyde and 0.5-1.5 equivalents of near infrared fluorescent dye SiB into another 2mL of N, N-dimethylformamide, fully mixing the two solutions after the two solutions are completely dissolved, then putting the two solutions into an ultrasonic cleaning machine, oscillating the two solutions for 4-6 min, then adding 6-8 mL of N, N-dimethylformamide, continuing to perform ultrasonic treatment for 20min to further stabilize nanoparticles in the suspension, then centrifuging the obtained suspension at 10000rpm for 4-6 min, abandoning the upper layer liquid, washing the lower layer solid with N, N-dimethylformamide for 2-3 times, then washing with anhydrous ethanol for 8-12 times, and finally, and (3) putting the obtained solid into a vacuum drying oven, and drying for 24 hours at room temperature to obtain an off-white solid, namely the fluorescent probe.
The near-infrared MOF fluorescent probe based on the silarhodamine has good spectral response performance to Adenosine Triphosphate (ATP). First, the fluorescence spectrum properties of the probe were investigated. Before the addition of ATP, the probe itself has no significant fluorescence emission; after addition of ATP, a distinct fluorescence emission peak appears in the near infrared region (670 nm). The near infrared fluorescence intensity of the probe molecule is continuously enhanced along with the increase of the ATP concentration. When 7mM ATP was added, the fluorescence intensity increased 8.5-fold, and thus the probe could be used to detect ATP. The fluorescence enhancement change of the probe is in a linear relation with the ATP concentration in the detection range of 1mM to 7mM, which indicates that the probe can reflect the ATP concentration by detecting the fluorescence intensity in the range. Next, the ultraviolet absorption spectrum of the probe was studied. When no ATP is added, the probe has no ultraviolet absorption; after addition of ATP, the probe shows an absorption peak at 640 nm. Next, the selectivity of the probe was investigated, and the probe was investigated for ions (P) commonly found in organisms, together with other nucleotides (ADP, AMP, GTP, CTP, UTP)3O10 5-,P2O7 4-,H2PO4 -,HPO4 2-,Cl-,SO4 2-,NO3 -,CH3COO-,CO3 2-) And the fluorescence response of the detector (ATP). As a result, ATP is found to cause a strong change in the fluorescence spectrum, and other analytes have little effect on the fluorescence spectrum of the probe. Then, the effect of pH on ATP measurement by the fluorescent probe was investigated, and when the pH was between 5.0 and 8.0, the effect of the fluorescent probe on ATP measurement was not affected. In addition, the fluorescent probe has quick response, and the response time is within 500 s.
An application of a triphosadenine near-infrared fluorescent probe. No significant fluorescence was observed in the control cells, and when a fluorescent probe was added to the cells, a stronger fluorescence was observed, indicating that the probe was able to detect the ATP present in the cells. When cells were pretreated with Apyrase (Apyrase) to remove ATP produced in the cells, a significant decrease in fluorescence was observed. These results illustrate that: the fluorescent probe can detect the change of ATP content in the cells. This provides a reliable means for monitoring the level of ATP within living cells.
Drawings
FIG. 1 is a schematic diagram of the preparation route and the interaction with ATP of the fluorescent probe.
FIG. 2 is a fluorescence spectrum of a fluorescent probe after it has been exposed to ATP at various concentrations.
The abscissa is wavelength and the ordinate is fluorescence intensity. The concentration of the fluorescent probe is 4mg/mL, and the ATP concentration is respectively as follows: 0,1.0,2.0,3.0,4.0,5.0,6.0,7.0 mM. The fluorescence excitation wavelength is 640nm, and the emission wavelength is 650nm-800 nm.
FIG. 3 is a graph of fluorescence linearity of fluorescent probe for different ATP concentrations.
FIG. 4 is a diagram showing UV-VIS absorption spectra before and after the action of a fluorescent probe with ATP.
The abscissa is wavelength and the ordinate is absorbance. The concentration of the fluorescent probe was 4mg/mL, and the ATP concentration was 7 mM.
FIG. 5 is a graph showing selectivity of fluorescent probes.
The concentration of the fluorescent probe was 4mg/mL, the ATP concentration was 7mM, and the other analyte concentrations were 7 mM.
FIG. 6 is a graph showing the effect of pH on fluorescent probes.
FIG. 7 is a graph showing the relationship between the fluorescence intensity of the fluorescent probe and the change with time after the action of ATP at different concentrations. The ATP concentrations were: 1.0,2.0,4.0,7.0 mM.
FIG. 8 is a diagram of cytotoxicity test. The abscissa is the concentration of the fluorescent probe and the ordinate is the survival rate of the cells.
FIG. 9(a) is a photograph of an image of a cell showing the interaction of a fluorescent probe with ATP; (b) relative fluorescence intensity plot.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments, but is not limited thereto.
Example 1:
preparation of fluorescent probes
The preparation method of the silicorhodamine near infrared fluorescent dye (SiB) comprises the following steps: at 0 ℃ N2Under protection, 2 equivalents of 3-Br-N, N-dimethylaniline was added to a 200mL two-necked round-bottomed flask containing 60mL of diethyl ether, and 2 equivalents of N-butyllithium were added thereto and reacted for 3 hours. 1 equivalent of dichlorodimethylsilane was dissolved in 10mL of diethyl ether, slowly added to the above reaction, and after the reaction was gradually returned to room temperature, the reaction was allowed to stand overnight, and 50mL of water was added to quench the reaction. The reaction mixture was extracted with ether, washed with brine, and dried over anhydrous sodium sulfate. The crude product was purified by silica gel column chromatography using petroleum ether/ethyl acetate (80:1) as eluent, and the solvent was distilled off under reduced pressure to give a pale yellow oily intermediate (yield 75%). Adding 10 equivalents of the intermediate product, 50 equivalents of 2-formylbenzoic acid and 1 equivalent of copper bromide into a 15mL sealed tube, and stirring and reacting at 140 ℃ for 5 hours; after cooling to room temperature, the reaction mixture was dissolved in dichloromethane, extracted with 2M NaOH solution, and the organic layer was washed with brine and dried over anhydrous sodium sulfate. The crude product was purified by silica gel column chromatography using petroleum ether, ethyl acetate and triethylamine (50:1:1) as eluent, and the solvent was distilled off under reduced pressure to give colorless needle-like crystals (yield 45%).1H NMR(400MHz,CDCl3)δ7.96(d,J＝7.5Hz,1H),7.64(t,J＝7.4Hz,1H),7.54(t,J＝7.5Hz,1H),7.30(d,J＝7.6Hz,1H),6.97(d,J＝2.9Hz,2H),6.78(d,J＝8.9Hz,2H),6.55(dd,J＝8.9,2.9Hz,2H),2.96(s,12H),0.64(s,3H),0.61(s,3H).
A preparation method of a near-infrared MOF fluorescent probe (ZIF-90@ SiB) based on silarhodamine comprises the following steps: as shown in fig. 1, at room temperature, adding 2mL of N, N-dimethylformamide into 100 equivalents of zinc acetate dihydrate to completely dissolve the zinc acetate, simultaneously, completely dissolving 200 equivalents of imidazole-2-formaldehyde and 1 equivalent of near infrared fluorescent dye SiB into another 2mL of N, N-dimethylformamide, when the two solutions are completely dissolved, fully mixing the two solutions, then placing the two solutions into an ultrasonic cleaning machine, oscillating for 5min, then adding 7mL of N, N-dimethylformamide, continuing to perform ultrasonic treatment for 20min to further stabilize the nanoparticles in the suspension, then centrifuging the obtained suspension at 10000rpm for 5min, discarding the upper layer of liquid, washing the lower layer of solid with N, N-dimethylformamide for 3 times, then washing with anhydrous ethanol for 10 times, and finally placing the obtained solid into a vacuum drying oven, and drying for 24 hours at room temperature to obtain an off-white solid, namely the fluorescent probe.
Example 2:
fluorescent probe and ATP solution preparation
Preparation of probe solution: a certain amount of the probe was weighed and dispersed in distilled water to prepare a 4mg/mL probe solution. Preparation of ATP solution: weighing a certain amount of adenosine-5' -disodium triphosphate, dissolving in distilled water to prepare a 20mM ATP solution, and storing in an environment at 4-8 ℃.
Example 3:
measurement of fluorescence Spectroscopy of the Effect of fluorescent Probe on ATP
FIG. 2 shows the fluorescence spectrum of the effect of the fluorescent probe on ATP, where the concentration of the fluorescent probe is 4mg/mL and the concentration of ATP is 0,1.0,2.0,3.0,4.0,5.0,6.0 and 7.0mM in this order. The excitation wavelength is fixed to be 640nm, and the emission wavelength range is 650-800 nm. The slit width was 5.0nm/5.0nm, and the fluorescence measuring instrument used was a Hitachi F4600 fluorescence spectrophotometer. As can be seen from FIG. 2, the fluorescent probe had no significant fluorescence emission before the addition of ATP; after addition of ATP, an emission peak appears in the near infrared region (670 nm). This is because ATP binds Zn constituting the probe structure2+Competitive coordination causes the zeolite imidazole structure of the probe to collapse, releasing the fluorophore SiB encapsulated therein, and emitting near infrared fluorescence. Meanwhile, the near infrared fluorescence intensity of the probe molecules is continuously enhanced along with the increase of the ATP concentration. When 7mM ATP was added, the fluorescence intensity increased 8.5-fold and thus could be used to detect ATP. FIG. 3 is a graph of the linear response of the probe to different ATP concentrations. When the ATP concentration is in the range of 1.0-7.0 mM, the fluorescence intensity of the probe and the ATP concentration present a linear relation, which indicates that the probe can quantitatively detect ATP in the concentration range.
Example 4:
determination of ultraviolet-visible absorption spectrum of fluorescent probe and ATP action
FIG. 4 is a graph showing UV-VIS absorption spectra of a fluorescent probe before and after the reaction with ATP, the concentration of the fluorescent probe being 4mg/mL and the amount of ATP added being 7 mM. The instrument for measuring the ultraviolet visible absorption spectrum is an Agilent Cary60 ultraviolet visible spectrophotometer. As can be seen in FIG. 4, there was no significant absorption of the probe without the addition of ATP; after ATP is added, the probe has an absorption peak at 640nm, and the absorption peak is consistent with the ultraviolet absorption peak of SiB, which shows that ATP causes collapse of the probe structure, so that fluorescent dye SiB is released, and ultraviolet absorption is generated.
Example 5:
selectivity of fluorescent probes for ATP determination
FIG. 5 is a graph of selectivity of fluorescent probes for ATP determination. Examination of the addition of ATP (7mM) and other nucleotides (ADP, AMP, GTP, CTP, UTP), and ions (P) common to organisms, to a fluorescent probe suspension at a concentration of 4mg/mL3O10 5-,P2O7 4-,H2PO4 -,HPO4 2-,Cl-,SO4 2-,NO3 -,CH3COO-,CO3 2-) (7mM) fluorescence response. As can be seen in FIG. 5, only ATP caused an 8.5-fold increase in fluorescence, while the other analytes had no significant effect on the fluorescence intensity of the probe. These results indicate that the fluorescent probe is better selective for ATP.
Example 6:
effect of solution pH on fluorescence Properties of fluorescent probes for measuring ATP
The influence of pH on the fluorescence spectrum of ATP measured by the fluorescent probe was examined, and the results are shown in FIG. 6. The pH range studied was 2.0-12.0, the concentration of the fluorescent probe was 4mg/mL, and the concentration of ATP was 7 mM. As can be seen from the figure, the fluorescence intensity of the fluorescent probe is basically unchanged when the pH value is 5.0-8.0, which indicates that the pH value in the range has no influence on the probe and ATP detection of the probe, and is a relatively proper pH value range. This is very advantageous for the use of the probe for the determination of ATP in real samples.
Example 7:
determination of response time of fluorescent Probe to ATP action
We investigated the response time of the fluorescent probe to ATP at concentrations of 1.0,2.0,4.0,7.0mM in sequence, and the results are shown in FIG. 7. As can be seen from the figure, the response time of the probe to various concentrations of ATP is within 500s, which can meet the requirement of real-time monitoring in actual samples. From FIG. 7, it can be seen that the fluorescence intensity reaches the maximum value and hardly changes any more in the following time, which indicates that the fluorescence probe has better light stability.
Example 8:
application of fluorescent probe in living cells
First, we performed cytotoxicity assays as shown in fig. 8. When 0-100 mug/mL of fluorescent probe is added, the survival rate of the cells is over 90 percent. This indicates that the fluorescent probe is less toxic and can be used to detect ATP in living cells. Then, we investigated the application of fluorescent probes in living cells, and selected HeLa cells for confocal microscopy, and the results are shown in fig. 9. In the control group cells, little fluorescence was observed. Intense fluorescence was then observed by adding the probe (4mg/mL) to the cells, indicating that the fluorescent probe acted on ATP in the cells, producing fluorescence. When cells were pretreated with ATP scavenger Apyrase (Apyrase) and then a probe was added, it was found that intracellular fluorescence was almost disappeared. These results indicate that the probe can detect the change of ATP content in cells, and provide a reliable means for monitoring the dynamic change of ATP level in living cells.
Claims (3)
1. The structure of the near-infrared MOF fluorescent probe based on the silarhodamine is composed of a nano-grade metal organic framework ZIF-90 and a near-infrared fluorescent dye SiB encapsulated inside.
2. The preparation method of the near-infrared MOF fluorescent probe based on the silarhodamine of claim 1 is characterized by comprising the following steps:
adding 2mL of N, N-dimethylformamide into 90-110 equivalents of zinc acetate dihydrate at room temperature to completely dissolve the zinc acetate dihydrate, simultaneously completely dissolving 180-220 equivalents of imidazole-2-formaldehyde and 0.5-1.5 equivalents of near-infrared fluorescent dye SiB into another 2mL of N, N-dimethylformamide, fully mixing the two solutions after the two solutions are completely dissolved, then putting the mixed solutions into an ultrasonic cleaning machine, oscillating for 4-6 min, subsequently adding 6-8 mL of N, N-dimethylformamide, continuing ultrasonic treatment for 20min to further stabilize nanoparticles in the suspension, then centrifuging the obtained suspension for 4-6 min at 10000rpm, discarding the lower-layer solid for 2-3 times by using the N, N-dimethylformamide, then washing for 8-12 times by using absolute ethyl alcohol, and finally, and (3) putting the obtained solid into a vacuum drying oven, and drying for 24 hours at room temperature to obtain an off-white solid, namely the fluorescent probe.
3. The application of the near-infrared MOF fluorescent probe based on the silarhodamine of claim 1, wherein the nano fluorescent probe can perform near-infrared fluorescence imaging detection on adenosine triphosphate in living cells.
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| CN116622367A (en) * | 2023-04-04 | 2023-08-22 | 浙江大学 | Composite fluorescent probe for detecting and imaging nitric oxide free radicals and synthesis method |
| CN116731335A (en) * | 2023-05-23 | 2023-09-12 | 河南中医药大学 | For As 5+ Ratio fluorescent probe RhB@UiO-67-NH with high selectivity 2 Preparation method and application thereof |
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