CN116731335B - For As 5+ Ratio fluorescent probe RhB@UiO-67-NH with high selectivity 2 Preparation method and application thereof - Google Patents
For As 5+ Ratio fluorescent probe RhB@UiO-67-NH with high selectivity 2 Preparation method and application thereof Download PDFInfo
- Publication number
- CN116731335B CN116731335B CN202310582549.5A CN202310582549A CN116731335B CN 116731335 B CN116731335 B CN 116731335B CN 202310582549 A CN202310582549 A CN 202310582549A CN 116731335 B CN116731335 B CN 116731335B
- Authority
- CN
- China
- Prior art keywords
- uio
- rhb
- fluorescent probe
- ratio fluorescent
- rhodamine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229940043267 rhodamine b Drugs 0.000 claims abstract description 55
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims abstract description 54
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 51
- 150000002500 ions Chemical class 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 25
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001514 detection method Methods 0.000 claims abstract description 14
- FYEKGZUXGKAJJQ-UHFFFAOYSA-N 3-amino-4-(4-carboxyphenyl)benzoic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C1=CC=C(C(O)=O)C=C1 FYEKGZUXGKAJJQ-UHFFFAOYSA-N 0.000 claims abstract 3
- 239000000975 dye Substances 0.000 claims abstract 2
- 239000011148 porous material Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 5
- 150000003841 chloride salts Chemical class 0.000 claims description 3
- 239000000523 sample Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 239000012429 reaction media Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000001338 self-assembly Methods 0.000 claims description 2
- 239000012621 metal-organic framework Substances 0.000 abstract description 9
- 239000002904 solvent Substances 0.000 abstract description 5
- 238000001308 synthesis method Methods 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 229910007926 ZrCl Inorganic materials 0.000 abstract 1
- 239000013110 organic ligand Substances 0.000 abstract 1
- 238000004458 analytical method Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- -1 arsenic ions Chemical class 0.000 description 6
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 229910052785 arsenic Inorganic materials 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 239000012491 analyte Substances 0.000 description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001917 fluorescence detection Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001277 hydride generation atomic absorption spectroscopy Methods 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 239000012229 microporous material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229910007746 Zr—O Inorganic materials 0.000 description 1
- 229940000489 arsenate Drugs 0.000 description 1
- AQLMHYSWFMLWBS-UHFFFAOYSA-N arsenite(1-) Chemical compound O[As](O)[O-] AQLMHYSWFMLWBS-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000005515 coenzyme Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000013289 nano-metal-organic framework Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010206 sensitivity analysis Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 150000003573 thiols Chemical group 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- 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
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention belongs to the technical field of metal organic frame materials, and particularly relates to a pair of As 5+ Ratio fluorescent probe RhB@UiO-67-NH with high selectivity 2 And its preparation method and application, introducing organic dye rhodamine B by direct synthesis method to make RhB and ZrCl 4 The two mixtures are combined with an organic ligand 2-amino-4, 4' -biphenyl dicarboxylic acid in DMF solvent to obtain a rhodamine B-loaded ratio fluorescent probe RhB@UiO-67-NH 2 Material, general purpose medicineOvergrowth of UiO-67-NH 2 The second fluorophore is introduced into the structure to promote UiO-67-NH 2 Fluorescence sensing properties of the metal organic framework material in 90% methanol, thereby allowing the metal organic framework to react with As in 90% methanol solution 5+ The ion has rapid and accurate specific recognition capability, stronger anti-interference capability, lower detection limit and good reproducibility.
Description
Technical Field
The invention belongs to the technical field of metal organic frame materials, and particularly relates to a pair of As 5+ Ratio fluorescent probe RhB@UiO-67-NH with high selectivity 2 And a preparation method and application thereof.
Background
Arsenic exists mainly in the form of inorganic and organic arsenic, such As arsenite (As 3+ ) And arsenate (As) 5+ ). As a contaminant widely existing in nature, arsenic is easily enriched in the human body through the food chain, in which As is absorbed by the human body 5+ The ions are converted into As 3+ The ions bind to enzymes, receptors and coenzymes having adjacent thiol pairs, inhibiting their biochemical functions and thus producing toxicity.
However, as in real environment 5+ The content of (c) is often low, and conventional detection techniques such as High Performance Liquid Chromatography (HPLC), atomic Absorption Spectrometry (AAS), ultraviolet spectrophotometry (UV), hydride generation-atomic absorption spectrometry (HG-AAS) and inductively coupled plasma mass spectrometry (ICP-MS) are often not effective in detecting arsenic ions at all times because of the disadvantages of expensive equipment, time consumption, poor portability, etc., even if arsenic ions can be detected at trace or trace levels. Therefore, the invention can rapidly detect As 5+ The fluorescent probe material of the ions has important significance.
Disclosure of Invention
The invention aims to provide a pair of As 5+ Ratio fluorescent probe RhB@UiO-67-NH with high ion selectivity 2 The preparation method and the application thereof effectively solve the problems of low efficiency, time consumption, easy interference, poor portability and the like of the traditional inspection method.
In order to achieve the above purpose, the invention adopts the following technical scheme:
for As 5+ Ratio fluorescent probe RhB@UiO-67-NH with high selectivity 2 The preparation method of (2) comprises the following steps: zr is Zr 4+ Is a chloride salt of (C), rhodamine B (RhB) and 2-amino-4, 4' -biphthalic acid (BPDC-NH) 2 ) Directly mixing together, using DMF organic solvent as reaction medium, forming UiO-67-NH containing supported rhodamine B through self-assembly process 2 And (3) modifying the material.
Further, the reaction temperature is 100 ℃, and the reaction time is 24 hours; rhodamine B and ligand BPDC-NH 2 The ratio of the amounts of the substances is 1:2 to 1:6.
Further, the rhodamine B, zr 4+ Chloride salt, 2-amino-4, 4' -biphthalic acid (BPDC-NH) 2 ) And DMF in an amount of 1:2:2: 900-1: 6:6:2719.
by using pairs of As 5+ Ratio fluorescent probe RhB@UiO-67-NH with high selectivity 2 The BET specific surface area of the probe prepared by the preparation method of (2) is 363-414 m 2 Per gram, langmuir specific surface area of 472-545 m 2 Per gram, pore volume of 0.344-0.388 cm 3 Per gram, the micropore volume is 0.088-0.104 cm 3 And/g, the average pore diameter is 3.342-3.878 nm.
For As 5+ Ratio fluorescent probe RhB@UiO-67-NH with high selectivity 2 For trace or trace detection of As 5+ Ions, which pair As in 90% methanol solution 5+ The detection limit of (2) is as low as 0.52. Mu.M.
The mechanism is as follows: the invention introduces rhodamine B into Zr by a direct synthesis method 4+ Chloride and 2-amino-)In the reaction system of 4,4' -biphenyl dicarboxylic acid, a metal organic framework with ratiometric fluorescence is obtained. The invention is realized by the method that the catalyst is prepared by the method of the invention in UiO-67-NH 2 The second kind of fluorophore rhodamine B is introduced into the structure to promote UiO-67-NH 2 Fluorescence sensing performance of the metal organic framework material in 90% methanol, thereby leading RhB@UiO-67-NH 2 Nanoscale metal-organic framework materials for As in 90% methanol solution 5 + The ion has rapid and accurate specific recognition capability, stronger anti-interference capability, lower detection limit and excellent regeneration performance. The invention provides a ratio fluorescent probe RhB@UiO-67-NH 2 Material pair As in 90% methanol solution 5+ The detection limit of the ions can be up to 0.52 mu M.
The invention has the advantages that: the ratio fluorescent probe RhB@UiO-67-NH of the invention 2 Metal organic framework material pair As 5+ The ion has the selective fluorescence detection capability, has lower detection limit, uses a solvothermal method and a direct synthesis method, is simple to operate and easy to synthesize, is suitable for large-scale industrial production, has higher research and application values, and has the advantages of good thermal stability, good chemical stability, good repeatability and the like.
Drawings
FIG. 1 is a comparative graph of nitrogen adsorption-desorption isotherms of the ratio fluorescent probes prepared in examples 1 to 3 of the present invention at 77K.
FIG. 2 is a ratio of fluorescent probes and raw UiO-67-NH prepared in examples 1-3 of the present invention 2 Is (4000 cm) -1 -400cm -1 )。
FIG. 3 is a ratio of fluorescent probes and raw UiO-67-NH prepared in examples 1-3 of the present invention 2 Is (1700 cm) -1 -400cm -1 )。
FIG. 4 is a ratio of fluorescent probes and raw UiO-67-NH prepared in examples 1-3 of the present invention 2 Is a comparison of the thermal stability of (a).
FIG. 5 shows fluorescence of the ratio fluorescent probe prepared in example 2 of the present invention to sense various concentrations of As 5+ Fluorescence emission spectrum after ion.
FIG. 6 is a graph showing the fluorescence of the ratio fluorescent probe prepared in example 2 of the present invention at a low concentration of fluorescence sensor As 5+ Linear fitting plot at ion.
FIG. 7 is a graph showing fluorescence intensity of the ratio fluorescent probe prepared in example 2 of the present invention after fluorescent sensing of different metal ions.
FIG. 8 is a ratio fluorescent probe fluorescence sensor As prepared in example 2 of the present invention 5+ Ion post regeneration intensity plot.
Detailed Description
Example 1
133.33mg of zirconium chloride (ZrCl) 4 0.573 mmoL) 147.47mg of 2-amino-4, 4' -biphthalic acid (BPDC-NH) 2 0.573 mmoL), 137.47mg rhodamine B (0.287 mmoL) was dissolved in 20mL DMF and sonicated. Transferring the solution into a 100mL polytetrafluoroethylene reaction kettle, putting the solution into an electrothermal constant-temperature air-blast drying oven, heating the solution for 30min from room temperature to 100 ℃, keeping the temperature at 100 ℃ for 24h, naturally cooling the solution to room temperature, taking out the solution in the reaction kettle, centrifuging the solution, immersing the solution in 50mL of DMF, replacing fresh DMF every 24h, repeating for three times, replacing the soaking solvent with methanol, replacing fresh methanol every 24h, and repeating for three times. Finally, centrifuging again to obtain pink crystals, simply drying, and placing the purified MOF in a vacuum drying oven at 100deg.C for 12h to obtain purified RhB@UiO-67-NH 2 A compound. Is marked as RhB@UiO-67-NH 2 (1:2)。
Example 2
133.33mg of zirconium chloride (ZrCl) 4 0.573 mmoL) 147.47mg of 2-amino-4, 4' -biphthalic acid (BPDC-NH) 2 0.573 mmoL), 68.49mg rhodamine B (0.143 mmoL) was dissolved in 20mL DMF and sonicated. Transferring the solution into a 100mL polytetrafluoroethylene reaction kettle, putting the solution into an electrothermal constant-temperature air-blast drying oven, heating the solution for 30min from room temperature to 100 ℃, keeping the temperature at 100 ℃ for 24h, naturally cooling the solution to room temperature, taking out the solution in the reaction kettle, centrifuging the solution, immersing the solution in 50mL of DMF, replacing fresh DMF every 24h, repeating for three times, replacing the soaking solvent with methanol, replacing fresh methanol every 24h, and repeating for three times. Finally, the mixture is centrifuged again to obtainThe obtained pink crystals are simply dried, and the purified MOF is placed in a vacuum drying oven at 100 ℃ for drying for 12 hours, thus obtaining the purified RhB@UiO-67-NH 2 A compound. Is marked as RhB@UiO-67-NH 2 (1:4)。
Example 3
133.33mg of zirconium chloride (ZrCl) 4 0.573 mmoL) 147.47mg of 2-amino-4, 4' -biphthalic acid (BPDC-NH) 2 0.573 mmoL), 45.74mg rhodamine B (0.095 mmoL) was dissolved in 20mL DMF and sonicated. Transferring the solution into a 100mL polytetrafluoroethylene reaction kettle, putting the solution into an electrothermal constant-temperature air-blast drying oven, heating the solution for 30min from room temperature to 100 ℃, keeping the temperature at 100 ℃ for 24h, naturally cooling the solution to room temperature, taking out the solution in the reaction kettle, centrifuging the solution, immersing the solution in 50mL of DMF, replacing fresh DMF every 24h, repeating for three times, replacing the soaking solvent with methanol, replacing fresh methanol every 24h, and repeating for three times. Finally, centrifuging again to obtain pink crystals, simply drying, and placing the purified MOF in a vacuum drying oven at 100deg.C for 12h to obtain purified RhB@UiO-67-NH 2 A compound. Is marked as RhB@UiO-67-NH 2 (1:6)。
Performance test:
(one) N 2 Adsorption-desorption analysis
For the synthesized UiO-67-NH at 77K 2 And the ratio fluorescent probe synthesized in examples 1 to 3 was subjected to nitrogen adsorption-desorption test. The specific surface area, micropore volume, total pore volume and average pore size results obtained are shown in Table 1.
TABLE 1UiO-67-NH 2 And different proportions of RhB@UiO-67-NH 2 Pore structure parameters of (a)
As can be seen from FIG. 1, uiO-67-NH is at relatively low pressure 2 And ratio fluorescent probe RhB@UiO-67-NH 2 The adsorption capacity of nitrogen gas is rapidly increased, and after a certain relative pressure is reached, the adsorption is saturated, which is a typical type I isotherm, and the reaction is thatMicropore filling phenomenon of microporous materials, which illustrates the UiO-67-NH synthesized by this experiment 2 And ratio fluorescent probe RhB@UiO-67-NH 2 Is a microporous material. Wherein, for the ratio fluorescent probe RhB@UiO-67-NH 2 When the relative pressure is greater than 0.9, the nitrogen adsorption amount continues to increase due to new pores formed by the agglomerated and accumulated material particles. Wherein for RhB@UiO-67-NH 2 The specific surface area shows a trend of increasing firstly and then reducing, and reaches the maximum when the ratio is 1:4, so that when the content of doped RhB is not very high, rhB and Zr ions can reach a proper coordination rate to form a coordination mode favorable for generating coordination bonds, and finally, the optimal coordination structure of RhB and Zr ions is reached in a proper ratio, when the content of RhB ions is increased, on one hand, partial pore channels can be blocked, on the other hand, structural defects can be caused, partial frameworks collapse is caused, and finally, the specific surface area is reduced. In summary, the ratio fluorescent probe RhB@UiO-67-NH with the largest specific surface area and total pore volume is selected by combining other pore structure parameters such as micropore volume, total pore volume and the like and comprehensively considering 2 (1:4) is the optimal material and is applied to the subsequent fluorescence sensing experiment.
(II) Infrared Spectrometry analysis
FIGS. 2 and 3 show UiO-67-NH 2 And RhB@UiO-67-NH 2 Is an infrared spectrum of (c). From the figure, uiO-67-NH can be obtained 2 In agreement with the reports in the literature, 3425cm -1 The characteristic peak corresponds to UiO-67-NH 2 Stretching vibration peak of middle N-H, 1536cm -1 、1415cm -1 The characteristic peak at the position corresponds to the telescopic vibration peak of carboxyl on benzene ring, 776cm -1 、662cm -1 The characteristic peak at the position corresponds to UiO-67-NH 2 Stretching vibration peak of Zr-O on skeleton, 1085cm -1 The characteristic peak at the position corresponds to the stretching vibration peak of Zr-OH. RhB@UiO-67-NH 2 With UIO-67-NH 2 In comparison, the wave number change was small and no new peak was found to appear, which suggests that RhB may be encapsulated in UiO-67-NH 2 In the pore canal, the host and guest body encapsulate the UiO-67-NH 2 The structural influence of (2) is less.
(III) thermal stability analysis
FIG. 4 is a diagram of UiO-67-NH 2 And ratio fluorescent probe RhB@UiO-67-NH 2 Thermal stability analysis graph of the material. As can be seen, the ratio fluorescent probe RhB@UiO-67-NH 2 Has better heat stability. At a temperature of between room temperature and 380 ℃, the ratio fluorescent probe RhB@UiO-67-NH 2 The first mass loss of the material (about 10%), mainly combined moisture and solvent molecules; at the temperature of 460-608 ℃, the ratio fluorescent probe RhB@UiO-67-NH 2 A second mass loss of the material (about 20%) occurs, at which temperature the material structure collapses. Whereas UiO-67-NH before modification 2 At 400 c the material structure begins to collapse. The above description shows that the ratio fluorescent probe RhB@UiO-67-NH 2 The material has good thermal stability.
(IV) fluorescence sensitivity analysis
Titration of varying concentrations of As 5+ The 90% methanol solution is tested by adopting a fluorescence spectrophotometer to test the RhB@UiO-67-NH of the invention 2 (1:4) nanoscale Material pair As 5+ Fluorescence sensing properties of ions. As shown in FIG. 5, with As 5+ Ion concentration increase, rhB@UiO-67-NH 2 (1:4) relative fluorescence intensity I of materials 452 /I 578 Gradually increasing, in the low concentration range, the linear dependence of the two can be calculated by equation I 452 /I 578 ＝S·[C]+1 analysis, I 452 To increase the fluorescence intensity of the material at 452nm after the addition of the analyte, I 578 For fluorescence intensity at 578nm of the material after addition of the analyte, C is the concentration of the added analyte in. Mu.M and S is the slope of the linear curve fit at low concentrations. As shown in FIG. 6, at low concentrations, I 452 /I 578 With As 5+ Has good linear relation between ion concentration (correlation coefficient R 2 = 0.99191), which indicates As 5+ The fluorescence enhancement effect of the ions well conforms to the equation model. Slope S is 1.2812 ×10 5 M -1 This indicates As 5+ Ion pair RhB@UiO-67-NH 2 The (1:4) material has strong fluorescence enhancement effect and high sensitivity, and meets the ratio fluorescence condition. By testing RhB@UiO-67-NH 2 (1:4) after multiple measurements in 90% methanol solutionFluorescence intensity, it was found that RhB@UiO-67-NH 2 (1: 4) the luminescence intensity in 90% methanol solution was kept substantially stable, and the standard deviation was calculated to be about 0.022, and the detection limit was calculated using the formula reported in the literature: lod=3δ/s=0.52 μΜ
In addition, for UiO-67-NH 2 Lod=3δ/s=118.3 μΜ. Therefore, after rhodamine B is introduced, the detection limit is reduced from 118.3 mu M to 0.52 mu M, and the sensitivity is obviously improved.
(fifth) fluorescence Selective analysis
At As 3+ 、Li + 、Cd 2+ 、Zn 2+ 、Pb 2+ 、Mn 4+ 、Co 2+ 、Ni 2+ 、Ag + 、K + 、Cr 3+ 、Na + 、Cu 2+ 、Fe 3+ Ratio fluorescent probe RhB@UiO-67-NH in presence of plasma 2 (1:4) pair As 5+ The fluorescence sensing properties of the ions are shown in FIG. 7. As can be seen from the graph, the ratio fluorescent probe RhB@UiO-67-NH of the invention even under the condition of the existence of other common metal ions and harmful elements 2 (1:4) pair As 5+ The ion fluorescence detection still has good selectivity, which shows that the ion fluorescence detection has good anti-interference capability on most common metal ions or harmful elements, and can be used for As 5+ And (3) ion fluorescence sensing.
Analysis of regeneration Performance
The reversibility of fluorescence of the material is a key factor for evaluating the performance of the sensor, and in order to explore the ratio fluorescent probe RhB@UiO-67-NH 2 (1:4) pair As 5+ The reusability of ion detection was studied for cyclic regeneration. Will be sensed by As 5+ The MOFs samples of (c) were centrifuged out and then washed continuously with 90% methanol to wash away as much as possible the surface-adhering metal ions. After sufficient drying, the next fluorescence sensing is performed. As shown in FIG. 8, it can be seen that after 4 cycles, the material pairs As 5+ The detection capability of the ions is hardly changed, which shows that the ratio fluorescent probe RhB@UiO-67-NH of the invention 2 (1:4) in detection of As 5+ Good reproducibility in application.
Claims (3)
1. For As 5+ Ratio fluorescent probe RhB@UiO-67-NH with high selectivity 2 The preparation method of (2) is characterized by comprising the following steps: zr is Zr 4+ Directly mixing the chloride salt of (C), rhodamine B and 2-amino-4, 4' -biphenyl dicarboxylic acid together, taking DMF organic solvent as a reaction medium, and forming UiO-67-NH containing organic dye RhB through a self-assembly process 2 A modified material; the reaction temperature is 100 ℃ and the reaction time is 24-30 hours; the rhodamine B, zr 4+ The ratio of the amounts of the substances of chloride, 2-amino-4, 4' -biphenyl dicarboxylic acid and DMF is 1:2:2: 900-1: 6:6:2719.
2. using the pair As of claim 1 5+ Ratio fluorescent probe RhB@UiO-67-NH with high selectivity 2 The probe prepared by the preparation method is characterized in that: BET specific surface area of 363-414 m 2 Per gram, langmuir specific surface area of 472-545 m 2 Per gram, pore volume of 0.344-0.388 cm 3 Per gram, the micropore volume is 0.088-0.104 cm 3 And/g, wherein the average pore diameter is 3.342-3.878 nm.
3. A probe according to claim 2 for the detection of As in micro-or trace amounts 5+ Ions, which pair As in 90% methanol solution 5+ The detection limit of (2) is as low as 0.52. Mu.M.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310582549.5A CN116731335B (en) | 2023-05-23 | 2023-05-23 | For As 5+ Ratio fluorescent probe RhB@UiO-67-NH with high selectivity 2 Preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310582549.5A CN116731335B (en) | 2023-05-23 | 2023-05-23 | For As 5+ Ratio fluorescent probe RhB@UiO-67-NH with high selectivity 2 Preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116731335A CN116731335A (en) | 2023-09-12 |
| CN116731335B true CN116731335B (en) | 2024-01-02 |
Family
ID=87917790
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310582549.5A Active CN116731335B (en) | 2023-05-23 | 2023-05-23 | For As 5+ Ratio fluorescent probe RhB@UiO-67-NH with high selectivity 2 Preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116731335B (en) |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105694849A (en) * | 2016-02-26 | 2016-06-22 | 浙江大学 | Rare-earth-free fluorescent powder for white light LED and preparation method of rare-earth-free fluorescent powder |
| BR112015022162A2 (en) * | 2014-09-16 | 2017-07-18 | Procter & Gamble | zinc fluorescent probe |
| CN107383386A (en) * | 2017-08-04 | 2017-11-24 | 南京工业大学 | Method for preparing two-dimensional metal organic framework material and application thereof |
| CN108192110A (en) * | 2018-02-26 | 2018-06-22 | 南昌大学 | Preparation method and its trivalent arsenic the detection application of rare earth metal organic frame fluorescence probe |
| JP2018145246A (en) * | 2017-03-02 | 2018-09-20 | 国立大学法人名古屋大学 | Sila dithieno rhodamine compound and fluorescent dye using the same |
| CN108641714A (en) * | 2018-08-22 | 2018-10-12 | 河南中医药大学 | Hg based on Rhodamine Derivatives2+Fluorescence probe and its preparation method and application |
| CN108929676A (en) * | 2018-07-02 | 2018-12-04 | 湖北大学 | A kind of preparation method of composition metal organic framework materials UiO-67 |
| CN109490267A (en) * | 2018-11-23 | 2019-03-19 | 西北师范大学 | It is enclosed with application of the UiO-66 of rhodamine 6G in fluorescence detection iron ion |
| CN113307982A (en) * | 2021-06-24 | 2021-08-27 | 河南中医药大学 | Preparation method and application of Cd/Zr-UIO-66 bimetallic organic framework material |
| CN114044915A (en) * | 2021-11-26 | 2022-02-15 | 河南中医药大学 | Preparation method and application of ratiometric fluorescent probe Eu/Zr-UiO-66 with high selectivity on cyclohexanone |
| CN114437709A (en) * | 2021-09-15 | 2022-05-06 | 中国科学院海洋研究所 | Nucleic acid functionalized MOF material and preparation and application thereof |
| CN114672302A (en) * | 2022-03-22 | 2022-06-28 | 湘潭大学 | Preparation and application of near-infrared MOF fluorescent probe based on silarhodamine |
| CN114858769A (en) * | 2022-04-25 | 2022-08-05 | 上海禹重实业有限公司 | Application of ratio type metal organic framework material in thiram detection |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735277B (en) * | 2010-01-15 | 2012-11-14 | 大连理工大学 | Fluorescent probe compounds, preparation method and use thereof |
-
2023
- 2023-05-23 CN CN202310582549.5A patent/CN116731335B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR112015022162A2 (en) * | 2014-09-16 | 2017-07-18 | Procter & Gamble | zinc fluorescent probe |
| CN105694849A (en) * | 2016-02-26 | 2016-06-22 | 浙江大学 | Rare-earth-free fluorescent powder for white light LED and preparation method of rare-earth-free fluorescent powder |
| JP2018145246A (en) * | 2017-03-02 | 2018-09-20 | 国立大学法人名古屋大学 | Sila dithieno rhodamine compound and fluorescent dye using the same |
| CN107383386A (en) * | 2017-08-04 | 2017-11-24 | 南京工业大学 | Method for preparing two-dimensional metal organic framework material and application thereof |
| CN108192110A (en) * | 2018-02-26 | 2018-06-22 | 南昌大学 | Preparation method and its trivalent arsenic the detection application of rare earth metal organic frame fluorescence probe |
| CN108929676A (en) * | 2018-07-02 | 2018-12-04 | 湖北大学 | A kind of preparation method of composition metal organic framework materials UiO-67 |
| CN108641714A (en) * | 2018-08-22 | 2018-10-12 | 河南中医药大学 | Hg based on Rhodamine Derivatives2+Fluorescence probe and its preparation method and application |
| CN109490267A (en) * | 2018-11-23 | 2019-03-19 | 西北师范大学 | It is enclosed with application of the UiO-66 of rhodamine 6G in fluorescence detection iron ion |
| CN113307982A (en) * | 2021-06-24 | 2021-08-27 | 河南中医药大学 | Preparation method and application of Cd/Zr-UIO-66 bimetallic organic framework material |
| CN114437709A (en) * | 2021-09-15 | 2022-05-06 | 中国科学院海洋研究所 | Nucleic acid functionalized MOF material and preparation and application thereof |
| CN114044915A (en) * | 2021-11-26 | 2022-02-15 | 河南中医药大学 | Preparation method and application of ratiometric fluorescent probe Eu/Zr-UiO-66 with high selectivity on cyclohexanone |
| CN114672302A (en) * | 2022-03-22 | 2022-06-28 | 湘潭大学 | Preparation and application of near-infrared MOF fluorescent probe based on silarhodamine |
| CN114858769A (en) * | 2022-04-25 | 2022-08-05 | 上海禹重实业有限公司 | Application of ratio type metal organic framework material in thiram detection |
Non-Patent Citations (8)
| Title |
|---|
| Amine-functionalized UiO-66 as a fluorescent sensor for highly selective detecting volatile organic compound biomarker of lung cancer;Zhang, ZJ等;《Journal of Solid State Chemistry》;第305卷;第122623页 * |
| Bimetallic Cd/Zr-UiO-66 material as a turn-on/off probe for As5+/Fe3+ in organic media;Geng, RC等;《CHEMOSPHERE》;第291卷(第1期);第132827页 * |
| Eu-MOF荧光猝灭法检测甲硝唑;刘宇霞;诸葛文凤;彭金云;;广州化工(第11期);第116-118页 * |
| The synthesis of a new aromatic polycarboxylic acid and its property as fluorescence-colorimetric chemosensor;Zhao, YC等;《JOURNAL OF MOLECULAR STRUCTURE 》;第 1251页 * |
| UiO系列金属-有机骨架的合成方法与应用;王学;王崇臣;王鹏;邢碧枞;;无机化学学报(第05期);第10-34页 * |
| 金属-有机框架材料的荧光探测应用进展;肖帆;崔元靖;钱国栋;;应用化学(第09期);第118-124页 * |
| 金属有机骨架材料作为荧光探针的研究进展;初红涛;姚冬;陈嘉琪;于淼;;材料导报(第13期);第146-158页 * |
| 锆基金属-有机骨架材料在异相催化中的应用;薛云;申妍铭;晏秘;程琥;庄金亮;;贵州师范大学学报(自然科学版)(第03期);第110-123页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116731335A (en) | 2023-09-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Hao et al. | Highly sensitive and selective fluorescent probe for Ag+ based on a Eu 3+ post-functionalized metal–organic framework in aqueous media | |
| He et al. | Determination of trace elements in food samples by ICP-AES after preconcentration with p-toluenesulfonylamide immobilized on silica gel and nanometer SiO 2 | |
| CN114196030B (en) | Preparation method and application of water-soluble macroporous zirconium porphyrin structure compound | |
| CN114044915B (en) | Preparation method and application of ratiometric fluorescent probe Eu/Zr-UiO-66 with high selectivity on cyclohexanone | |
| Guo et al. | One-pot synthesis of a carbon dots@ zeolitic imidazolate framework-8 composite for enhanced Cu 2+ sensing | |
| CN106546571B (en) | Method for detecting polycyclic aromatic hydrocarbon in liquid phase | |
| Zhang et al. | Floral and lamellar europium (iii)-based metal–organic frameworks as high sensitivity luminescence sensors for acetone | |
| Zhong et al. | Turn-on fluorescent sensor based on curcumin@ MOF-5 for the sensitive detection of Al 3+ | |
| CN110483746B (en) | Synthesis of novel covalent organic framework material and application of novel covalent organic framework material in metal ion recognition and dye adsorption | |
| CN114539605A (en) | Sponge-supported porphyrin covalent organic framework integrated material and preparation method and application thereof | |
| CN113929905B (en) | Preparation method and application of imine bond-connected fluorescent covalent organic framework | |
| CN113307982B (en) | Preparation method and application of Cd/Zr-UIO-66 bimetallic organic framework material | |
| CN108854974A (en) | A kind of difunctional core-shell nano flower composite material of intelligence and preparation method and application | |
| CN108623815B (en) | Preparation method of cadmium-based metal organic framework material and application of cadmium-based metal organic framework material in ion recognition | |
| Dong et al. | A quinoline group modified SBA-15 INHIBIT logic gate with [Cu2+ and Zn2+] or [Cu2+ and Cd2+] as inputs | |
| CN116731335B (en) | For As 5+ Ratio fluorescent probe RhB@UiO-67-NH with high selectivity 2 Preparation method and application thereof | |
| CN109596593B (en) | Method for detecting nitrofuran antibiotics or quinolone antibiotics in drinking water | |
| CN113461961B (en) | For Fe3+High-selectivity Ag/Zn-ZIF-8 bimetal organic framework material | |
| CN113912856B (en) | Water-stable microporous dual-function MOFs material and preparation method and application thereof | |
| CN117940209A (en) | Zirconium-based metal organic framework serving as heavy metal adsorbent in condensate and preparation method thereof | |
| CN110951085B (en) | Preparation of Cd-MOF and application of Cd-MOF in fluorescent recognition of DMSO and capture of CO2In (1) | |
| Liu et al. | Granular Ln-MOF@ Activated Carbon Composite for Highly Selective and Sensitive Detection of Cr3+ Cations | |
| CN113121842B (en) | Zirconium-based metal organic framework material, preparation and application thereof in nitrofuran antibiotic treatment | |
| CN115010942B (en) | Preparation method and application of ratiometric fluorescent probe Tb-UiO-66 with high selectivity on styrene | |
| CN117924737B (en) | Terbium-based MOF crystal material, preparation method thereof, thin film fluorescence sensor and nitrophenol detection application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |