CN108517207A - Tb-MOFs PA fluorescent detection probes and the preparation method and application thereof - Google Patents
Tb-MOFs PA fluorescent detection probes and the preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a kind of Tb MOFs PA fluorescent detection probes, chemical formula is as follows：{(C2H6NH2)2[Tb2(ptptc)2(DMF)(H2O)]·DMF·6H2O } n, the invention also discloses the preparation method of above-mentioned detection probe, process is, by six nitric hydrate terbiums, 3,3 ', 5,5 ' terphenyl tetrabasic carboxylic acids, HNO3, N, N dimethylformamides and deionization be added in the polytetrafluoroethylliner liner of hydrothermal synthesis kettle, stir evenly, mixed solution；The mixed solution of gained is encapsulated and is put into reaction kettle, then reaction kettle is put into baking oven and is heated to 160 DEG C, reacts 72h；Reaction kettle is taken out from baking oven, temperature will be room temperature, by the mixed solution after reaction using DMF washings, it is dry to get.Probe produced by the present invention has the characteristics that good selectivity, high sensitivity, fast response time.
Description
Technical field
The invention belongs to chemical sensitisation technical fields, and in particular to Tb-MOFs PA fluorescent detection probes, the present invention also relate to
And the preparation method of the detection probe is in application.
Background technology
2,4,6- trinitrophenols also known as picric acid (Picric Acid are all made of write a Chinese character in simplified form PA below), are widely used in
Manufacture electric cap, fireworks, shell and dyestuff, medicine, leather etc..2,4,6- trinitrophenols are soluble easily in water, a large amount of to use meeting
Serious water body and soil pollution are caused, long-term a large amount of contact PA can cause dizziness, have a headache, induce dermatitis and cause liver, kidney
Damage.In addition PA causes high risks as a kind of high explosive, low-security high explosives to public safety.
Instrument detection method such as high performance liquid chromatography, Raman spectroscopy, mass spectrography etc. is the main method of PA detections.So
And there are still some intrinsic problems for such method, such as the large-scale instrument of needs costliness, detecting and selecting property are poor, testing cost height.
Fluorescence probe detection method have the characteristics that corresponding rapid, easy to operate, selection it is single-minded more meet it is real-time, efficient, highly selective
Detection demand.
Invention content
The object of the present invention is to provide a kind of Tb-MOFs PA fluorescent detection probes, which has selectivity good, sensitive
The characteristics of degree height, fast response time.
It is a further object to provide a kind of preparation methods of Tb-MOFs PA fluorescent detection probes.
The technical solution adopted in the present invention is Tb-MOFs PA fluorescent detection probes, and chemical formula is as follows：
{(C2H6NH2)2[Tb2(ptptc)2(DMF)(H2O)]·DMF·6H2O}n。
Second technical solution of the present invention is the preparation method of Tb-MOFs PA fluorescent detection probes, specifically
Include the following steps：
Step 1, by six nitric hydrate terbiums, 3,3 ', 5,5 '-terphenyl tetrabasic carboxylic acids, HNO3, N,N-dimethylformamide and go
Ion is added in the polytetrafluoroethylliner liner of hydrothermal synthesis kettle, is stirred evenly, mixed solution；
Step 2, the mixed solution obtained by step 1 is encapsulated and is put into reaction kettle, then reaction kettle is put into baking oven
160 DEG C are heated to, and mixed solution is made to react 72h in reaction kettle；
Step 3, reaction kettle is taken out from baking oven, temperature will be room temperature, by the mixed solution after reaction from reaction kettle
Take out, using DMF washings, it is dry to get.
The invention has the advantages that the corresponding type PA detection probes of fluorescence produced by the present invention, it can be strong according to fluorescence probe
The variation of degree carries out visualization and differentiates PA in real time；PA concentration can be measured using Fluorescence Spectrometer and quantitatively, detection line is reachable
100 nanomoles, solve specific recognition capability present in existing PA detection techniques it is low, detection it is complicated for operation, detection it is sensitive
Spend low technological deficiency.
Description of the drawings
Fig. 1 (a) is the asymmetric cell structure chart of Tb-MOFs PA fluorescent detection probes of the present invention；
Fig. 1 (b) is that two carboxylate radical bridgings of Tb-MOFs PA fluorescent detection probes of the present invention form bimetallic [Tb2(μ2-
COO)2(COO)6]2-The structural unit figure of cluster base；
Fig. 2 (a) is Tb-MOFs PA fluorescent detection probes of the present invention two-dimensional layered structure figure on the faces ab；
Fig. 2 (b) is the three-dimensional frame structure figure that Tb-MOFs PA fluorescent detection probes of the present invention are presented on the faces bc；
Fig. 2 (c) is Tb-MOFs PA fluorescent detection probes of the present invention has one-dimensional tunnel structure figure in the directions b；
Fig. 3 is the powder diffraction test spectrogram of Tb-MOFs PA fluorescent detection probes of the present invention；
Fig. 4 is Tb-MOFs PA fluorescent detection probe and ligand H of the present invention4Ptptc solid fluorescence spectrograms；
Fig. 5 is tested different analyte identification selections using the methanol Tb-MOFs PA fluorescent detection probes of 1mg/mL
Figure；
Fig. 6 is that lower identification selection coexists in PA and other analytes using the methanol Tb-MOF fluorescence probes system of 1mg/mL
Property test chart；
Fig. 7 is the methanol Tb-MOF fluorescence probes system using 1mg/mL to PA fluorescence response time test figures；
Fig. 8 is the methanol Tb-MOF fluorescence probes system using 1mg/mL to various concentration PA response test figures；
Fig. 9 is nonlinear fitting of the methanol Tb-MOF fluorescence probes system to various concentration PA fluorescence responses of 1mg/mL
Figure.
Specific implementation mode
The following describes the present invention in detail with reference to the accompanying drawings and specific embodiments.
Tb-MOFs PA fluorescent detection probes of the present invention, chemical formula are as follows：{(C2H6NH2)2[Tb2(ptptc)2(DMF)
(H2O)]·DMF·6H2O}n。
In formula, H4Ptptc be terphenyl -2,2 ', 4,4 '-tetrabasic carboxylic acids；The metal-organic framework belongs to anorthic system,
Space group, there are two dimethylamine cations in structure, thus the crystal structure is the three-dimensional anion for having one-dimensional channels
Frame.There are the Tb of two kinds of coordination environments in crystal structure3+, wherein Tb13+Coordination mode and Tb23+It is similar, Tb13+With
Tb23+All it is and the Tb1 by being coordinated with 6 carboxylate oxygen atoms chelated, Liang Ge overseas Chinese federations carboxylate oxygen atoms and to form eight-coordinate structure3 +It is coordinated and Tb2 with a DMF again3+With a H2O is coordinated the tetrakaidecahedron structure to form nine coordinations.The Tb1 in crystal structure3+
With Tb23+The list of coordination units of formation forms bimetallic [Tb by two carboxylate radical bridgings2(μ2-COO)2(COO)6]2-Cluster base,
ptptc4-The carboxyl of ligand is with μ6The adjacent bimetallic cluster base of coordination mode connection is formed and two-dimensional layered structure；μ4Bridging is coordinated
The ptptc of pattern4-Ligand connects adjacent two-dimensional layer and forms the 3-dimensional metal organic framework with one-dimensional channels.The crystal
Structure has the one-dimensional channels of quadrangle in the directions a, and aperture isIn the directions b, there is the sums of a quadrangle
The duct of one parallelogram, aperture are respectivelyWithDuct can there is diformazans
Amine cation and solvent molecule, it is 35% to calculate hole ratio by PLATON.
The present invention also provides Tb-MOFs (Tb-MOFs is the abbreviation of terbium metal organic frame) PA fluorescent detection probes
Preparation method, Tb-MOFs classes PA fluorescent detection probes preparation method provided by the invention using six nitric hydrate terbiums as source metal, with
3,3 ', 5,5 '-terphenyl tetrabasic carboxylic acid (H4Ptptc it is) ligand, dinethylformamide (DMF, 4mL) and deionization (4mL) are
Solvent specifically includes following steps：
Step 1, by 8.7mg, six nitric hydrate terbiums of 0.02mmol, 4mg, 0.01mmol3,3 ', 5,5 '-terphenyl tetrabasic carboxylic acids
(H4Ptptc), three drop 6mol/L HNO3, N,N-dimethylformamide (DMF) and 4ML deionizations are added to 25ML hydrothermal synthesis kettles
Polytetrafluoroethylliner liner in, stir evenly；
Step 2, the mixed solution obtained by step 1 is encapsulated and is put into reaction kettle, then reaction kettle is put into baking oven
160 DEG C are heated to, and mixed solution is made to react 72h in reaction kettle；
Step 3, reaction kettle is taken out from baking oven, temperature will be room temperature, by the mixed solution after reaction from reaction kettle
Take out, using DMF washings, it is dry to get.
The above-mentioned Tb-MOFs probe applications being prepared are in the fluorescence identifying of PA.
The application method of Tb-MOFs PA fluorescent detection probes provided by the invention has no specifically limited.It usually can be in room
Probe molecule is dispersed in ethyl alcohol, methanol, N,N-dimethylformamide equal solvent under temperature and is tested.To study the probe point
Son acts on the specific recognition of PA molecules, is the probe solution of 1mg/mL by solvent compound concentration of methanol；It prepares respectively
The paranitrobenzoic acid (PNBA) of 10mM, meta nitro aniline (m-NA), ortho-nitraniline (o-NA), o-nitrophenol (o-NP),
2,4,6- trinitrophenols (PA), nitrobenzene (NB), 2,4 dinitrophenyl hydrazine (NB), benzene (benzene), phenol (phenol),
Aniline (aniline), the methanol or ethanol solution of niacin (3-NC).
50 μM of above-mentioned different organic compounds are added in the methanol Tb-MOFs fluorescence probe systems of 2mL 1mg/mL to carry out
The selectivity test of probe molecule；50 μM PA and 50 μM is added in the methanol Tb-MOFs fluorescence probe systems of 2mL 1mg/mL
Above-mentioned difference organic compound carries out the mixing selectivity test of probe molecule；In the methanol Tb-MOFs fluorescence of 2mL 1mg/mL
1 μM, 10 μM, 100 μM and 200 μM of the 30 seconds record system fluorescence intensities in the intervals PA are added in probe system, are detected response
Time test；0.1-200 μM of PA is added in the methanol Tb-MOFs fluorescence probe systems of 2mL 1mg/mL and carries out concentration-response
Test.
The probe generates response for the PA of 0.1-200 μM of concentration, and good non-linear relation (R is presented2=0.9994).
Fluorescence detection method can be used in the concentration range, quantitative detection is carried out to PA, PA minimal detectable concentrations are 100nM (excitation waves
A length of 325nm)；The probe has the effect of detecting immediately, and the corresponding time is less than 30 seconds.
Embodiment 1
The preparation of Tb-MOFs PA fluorescent detection probes
By six nitric hydrate terbiums (8.7mg, 0.02mmol), 3,3 ', 5,5 '-terphenyl tetrabasic carboxylic acids (4mg, 0.01mmol), 3
Drip 6mol/L HNO3, N,N-dimethylformamide (4mL) and deionization (4mL) are added to the polytetrafluoro of 25mL hydrothermal synthesis kettles
In ethylene liner, stir evenly；It by above-mentioned prepared mixed solution encapsulation, is put into reaction kettle, reaction kettle is put into baking oven, adds
Heat is warming up to 160 DEG C, reacts 72h；Be filtered, washed, dry white crystal is Tb-MOFs fluorescence probe materials.
The above-mentioned functional metal based on rare earth metal cluster being prepared-organic backbone is subjected to structure, purity and glimmering
Light characterizes：
1) Tb-MOFs structured testings
Single crystal diffraction data carry out data collection in 150k using Bruker D8Venture diffractometers with Mo/K а raysIt is collected with the θ scan modes of ω/2, absorption correction uses SADABS programs.With direct method solution structure, then
Whole non-hydrogen atom coordinates are found out with difference Fourier method.Evaluation work is completed in PC machine with SHELXTL program bags.It is detailed
Crystallographic data is shown in Table 1, and structure is shown in attached drawing 1-2；Wherein Fig. 1 (a) indicates that Tb-MOF 2,4,6- trinitrophenol fluoroscopic examinations are visited
The asymmetric cell structure chart of needle；Fig. 1 (b) indicates two carboxylate radicals of Tb-MOF2,4,6- trinitrophenol fluorescent detection probes
Bridging forms bimetallic [Tb2(μ2-COO)2(COO)6]2-The structural unit figure of cluster base.Fig. 2 (a) indicates Tb-MOF 2,4,6- tri-
Nitrophenol fluorescent detection probe two-dimensional layered structure figure on the faces ab；Fig. 2 (b) indicates Tb-MOF 2,4,6- trinitrophenols
The three-dimensional frame structure figure of fluorescent detection probe presented on the faces bc；Fig. 2 (c) indicates Tb-MOF 2,4,6- trinitrophenols
Fluorescent detection probe has one-dimensional channels figure in the directions b.
Table 1
aR1=Σ | | Fo|-|Fc||/Σ|Fo|.bwR2=[Σ [w (Fo 2-Fc 2)2]/Σw(Fo 2)2]1/2, where w=1/
[σ2(Fo)2+(aP)2+ bP] and P=(Fo 2+2Fc 2)/3.
The structure of Fig. 1 and Fig. 2 shows：Tb-MOFs is crystal structure, belongs to anorthic system,Space group；The crystal knot
Structure is functional metal-organic backbone based on rare earth metal cluster, and there are the Tb of two kinds of coordination environments in crystal structure3+, two
The Tb of kind coordination environment3+[Tb is formed by carboxylate radical bridging2(μ2-COO)2(COO)6]2-Bimetallic cluster base, wherein Tb13+'s
Coordination mode and Tb23+It is similar, Tb13+And Tb23+All it is by the carboxylate oxygen atoms with 6 chelatings, two bridging carboxylic acid oxygen
Atomic coordinate formation eight-coordinate structure, and Tb13+It is coordinated and Tb2 with a DMF again3+With a H2O is coordinated to form the ten of nine coordinations
Tetrahedral structure.The Tb1 in crystal structure3+With Tb23+The list of coordination units of formation forms bimetallic by two carboxylate radical bridgings
Cluster base, ptptc4-The carboxyl of ligand is with μ6The adjacent bimetallic cluster base of coordination mode link forms two-dimensional layered structure；μ4Bridge
The even ptptc of coordination mode4-Ligand links adjacent two-dimensional layer and forms the 3-dimensional metal organic framework with one-dimensional channels.
The crystal structure has the one-dimensional channels of quadrangle in the directions a, while there is the parallel with one of quadrangle in the directions b
The duct of quadrangle, duct can there is dimethylamine cations and solvent molecule.
2) Tb-MOFs PA fluorescent detection probes powder diffraction test (PXRD)：
By Tb-MOFs fluorescence probes produced by the present invention at room temperature on Brooker D8 ADVANCE powder diffractometers
(Bruker D8 ADVANCE X-Ray Diffractometer) is tested, spectrogram such as Fig. 3.Test spectrogram main diffraction peak and base
It coincide in crystal data simulation peak, illustrates that Tb-MOFs obtained by above-mentioned preparation has preferable purity.Abscissa 2theta/ in Fig. 3
Degree is X-ray diffractometer with the entire diffraction region of the angle scanning of 2 θ, and the abscissa as X-ray diffraction spectrum exists,
The intensity of the diffraction maximum of different angle of diffraction is as ordinate.
3) Tb-MOFs PA fluorescent detection probes solid fluorescence is tested
The Tb-MOFs fluorescence probes that the present invention is prepared are at room temperature in Agilent Fluorescence Spectrometer (Agilent
Cary Eclipse fluorescence spectrophotometer) on test, excitation wavelength 325nm, spectrogram such as Fig. 4,
As shown in Figure 4, it is respectively 363nm that the above-mentioned Tb-MOFs fluorescence probes being prepared, which mainly have 5 fluorescence emission peaks, position,
491nm, 546nm, 586nm and 621nm.Above-mentioned fluorescence emission peak can be attributed to ligand π-π * transition and terbium respectively5D4→7F6,5D4→7F5,5D4→7F4and 5D4→7F3Characteristic emission peak.
Embodiment 2：
The present embodiment is Tb-MOFs probes made from embodiment 1, to the response test of single group analyte.
The Tb-MOFs probe suspensions that methanol is 1mg/mL for solvent compound concentration are used, then respectively to the above-mentioned probes of 2mL
Add 50 μM of paranitrobenzoic acids (PNBA), meta nitro aniline (m-NA), ortho-nitraniline (o-NA), o-nitrophenol in suspension
(o-NP), 2,4,6- trinitrophenols (PA), nitrobenzene (NB), 2,4-dinitrophenylhydrazine (2,4-DNPH), benzene (Benzene),
Phenol (Phenol), aniline (Aniline), niacin (3-NC).Probe suspension is measured to be added before and after different knot organic molecules
Relative intensity of fluorescence, the results are shown in Figure 5 (F0For not plus organic molecule suspension relative intensity of fluorescence, F be added it is organic
The relative intensity of fluorescence of suspension after molecule).From figure 5 it can be seen that only added with the probe solution of PA, fluorescence significantly subtracts
It is weak.Other structures analog and probe molecule are without obvious effect compared with PA.The present embodiment experimental results show, the spy
Needle molecule can be identified specifically and detect PA.
Embodiment 3
The present embodiment is Tb-MOFs probes made from embodiment 1, and the response test of object is analysed to bi-component.
The Tb-MOFs probe suspensions that methanol is 1mg/mL for solvent compound concentration are used, then are divided outstanding to the above-mentioned probes of 2mL
Add 50 μM of PA and paranitrobenzoic acid (PNBA), meta nitro aniline (m-NA), ortho-nitraniline (o-NA), adjacent nitre in turbid
Base phenol (o-NP), 2,4,6- trinitrophenols (PA), nitrobenzene (NB), 2,4-dinitrophenylhydrazine (2,4-DNPH), benzene
(Benzene), phenol (Phenol), aniline (Aniline), any one of niacin (3-NC).Probe suspension is measured to add
Enter the relative intensity of fluorescence before and after analyte, the results are shown in Figure 6 (F0Not add the suspension relative intensity of fluorescence of analyte, F
For the suspension relative intensity of fluorescence after two-component analyte is added).From fig. 6 it can be seen that other analytes not shadow is added
Probe is rung to PA recognition reactions.The present embodiment experimental results show that the probe molecule specifically can be identified and be detected
Go out PA.Analyte indicates analyte.
Embodiment 4：
The present embodiment is Tb-MOFs probes made from embodiment 1, is tested the various concentration PA response times.
The Tb-MOFs probe suspensions that methanol is 1mg/mL for solvent compound concentration are used, to the above-mentioned probe suspensions of 2mL
In be separately added into 1 μM, 10 μM, 100 μM and 200 μM PA.A fluorescence probe intensity was recorded every 30 seconds, as a result such as Fig. 7 institutes
Show, abscissa is the time that PA is added, and ordinate is relative intensity of fluorescence.As can be seen from Figure 7：After PA is added, in 30 seconds
Through complete response.The present embodiment experimental results show that the probe molecule can rapidly have an effect with PA, provide fluorescence
Signal intensity can be used for the real-time monitoring of PA.
Embodiment 5：
The present embodiment is Tb-MOFs probes made from embodiment 1, to the response test of various concentration PA.
The Tb-MOFs probe suspensions that methanol is 1mg/mL for solvent compound concentration are used, to the above-mentioned probe suspensions of 2mL
In plus 0.1-200 μM of PA.Measure the relative intensity of fluorescence that probe suspension is added before and after analyte, the results are shown in Figure 8 (F0
It is the suspension relative intensity of fluorescence being added after two-component analyte not add the suspension relative intensity of fluorescence of analyte, F).
As can be seen from Figure 8, Tb-MOFs fluorescence probes intensity is reduced rapidly with the increase of PA concentration, and minimal detectable concentration reaches
100nM.The present embodiment experimental results show that the fluorescence probe intensity responds the increase of PA concentration good.
Embodiment 6：
The present embodiment is Tb-MOFs probes made from embodiment 1, to the non-of the fluorescence response test result of various concentration PA
Linear fit.
The Tb-MOFs probe suspensions that methanol is 1mg/mL for solvent compound concentration are used, to the above-mentioned probe suspensions of 2mL
In plus 0.1-200 μM of PA.Measure the relative intensity of fluorescence that probe suspension is added before and after analyte, the results are shown in Figure 8 (F0
It is the suspension relative intensity of fluorescence being added after two-component analyte not add the suspension relative intensity of fluorescence of analyte, F).
It maps to PA concentration with gained fluorescence intensity in Fig. 8 and carries out nonlinear fitting and obtain Fig. 9.As shown in Figure 9, in a concentration of 0.1- of PA
Within the scope of 200 μM, good non-linear relation is presented with PA concentration in fluorescence probe intensity.The nonlinear equation is： It is real obtained by the present embodiment
It tests the results show that the probe has the application potential for quantitatively detecting PA.
The characteristics of Tb-MOFs PA fluorescent detection probes of the present invention is that can be visualized according to the variation of fluorescence probe intensity
Differentiate PA；Can PA be measured to real-time qualitative using Portable fluorescence spectrometer, solved special present in existing PA detection techniques
Anisotropic recognition capability is low, detection is complicated for operation, the deficiencies of can not monitoring in real time.
Claims (3)
1.Tb-MOFs PA fluorescent detection probes, it is characterised in that：Chemical formula is as follows：
{(C2H6NH2)2[Tb2(ptptc)2(DMF)(H2O)]·DMF·6H2O}n。
2. the preparation method of Tb-MOFs PA fluorescent detection probes as described in claim 1, it is characterised in that：Specifically include with
Lower step：
Step 1, by six nitric hydrate terbiums, 3,3 ', 5,5 '-terphenyl tetrabasic carboxylic acids, HNO3, N,N-dimethylformamide and deionization
Be added in the polytetrafluoroethylliner liner of hydrothermal synthesis kettle, stir evenly, mixed solution；
Step 2, the mixed solution obtained by step 1 is encapsulated and is put into reaction kettle, then reaction kettle is put into baking oven and is heated
160 DEG C are warming up to, and mixed solution is made to react 72h in reaction kettle；
Step 3, reaction kettle to be taken out from baking oven, temperature will be room temperature, and the mixed solution after reaction is taken out from reaction kettle,
Using DMF washings, it is dry to get.
3. a kind of purposes of Tb-MOFs PA fluorescent detection probes as described in claim 1, it is characterised in that：In the fluorescence of PA
Application in identification.
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| CN110951084A (en) * | 2018-09-27 | 2020-04-03 | 天津工业大学 | Application of white-light-emitting double-rare-earth metal organic framework material in detection of phenol pollutants |
| CN112646191A (en) * | 2019-10-12 | 2021-04-13 | 中国科学院福建物质结构研究所 | Rare earth-organic framework nano fluorescent probe and preparation method and application thereof |
| CN114509416A (en) * | 2022-01-21 | 2022-05-17 | 浙江大学 | Fluorescent array sensor for distinguishing nitrophenol compounds and preparation method thereof |
| CN114957689A (en) * | 2022-05-23 | 2022-08-30 | 集美大学 | Gallate fluorescent probe, preparation method thereof and fluorescence analysis method |
| CN115181285A (en) * | 2022-07-12 | 2022-10-14 | 延安大学 | Terbium coordination polymer crystal and preparation method and application thereof |
| CN117924737A (en) * | 2024-03-25 | 2024-04-26 | 德州学院 | Terbium-based MOF crystal material, preparation method thereof, thin film fluorescence sensor and nitrophenol detection application |
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| CN106916317A (en) * | 2017-02-27 | 2017-07-04 | 三峡大学 | A kind of Rare Earth Europium base organic crystalline material, prepares and the application on fluorescence identifying antibiotic |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110951084A (en) * | 2018-09-27 | 2020-04-03 | 天津工业大学 | Application of white-light-emitting double-rare-earth metal organic framework material in detection of phenol pollutants |
| CN109142304A (en) * | 2018-09-30 | 2019-01-04 | 武汉大学 | A kind of pH visualization ratio fluorescent Sensors & Application based on bimetallic organic backbone nano-complex |
| CN109142304B (en) * | 2018-09-30 | 2021-01-01 | 武汉大学 | pH visual ratio fluorescence sensor based on bimetallic organic framework and application |
| CN112646191A (en) * | 2019-10-12 | 2021-04-13 | 中国科学院福建物质结构研究所 | Rare earth-organic framework nano fluorescent probe and preparation method and application thereof |
| CN112646191B (en) * | 2019-10-12 | 2022-03-22 | 中国科学院福建物质结构研究所 | Rare earth-organic framework nano fluorescent probe and preparation method and application thereof |
| CN114509416A (en) * | 2022-01-21 | 2022-05-17 | 浙江大学 | Fluorescent array sensor for distinguishing nitrophenol compounds and preparation method thereof |
| CN114957689A (en) * | 2022-05-23 | 2022-08-30 | 集美大学 | Gallate fluorescent probe, preparation method thereof and fluorescence analysis method |
| CN115181285A (en) * | 2022-07-12 | 2022-10-14 | 延安大学 | Terbium coordination polymer crystal and preparation method and application thereof |
| CN117924737A (en) * | 2024-03-25 | 2024-04-26 | 德州学院 | Terbium-based MOF crystal material, preparation method thereof, thin film fluorescence sensor and nitrophenol detection application |
| CN117924737B (en) * | 2024-03-25 | 2024-06-21 | 德州学院 | Terbium-based MOF crystal material, preparation method thereof, thin film fluorescence sensor and nitrophenol detection application |
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