CN111303193B - PADAP derivative, preparation method and application thereof - Google Patents

PADAP derivative, preparation method and application thereof Download PDF

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CN111303193B
CN111303193B CN202010243455.1A CN202010243455A CN111303193B CN 111303193 B CN111303193 B CN 111303193B CN 202010243455 A CN202010243455 A CN 202010243455A CN 111303193 B CN111303193 B CN 111303193B
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uranyl
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王宏青
伍徐孟
黄秋香
尹强
王榆元
胡清华
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University of South China
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Abstract

The invention provides a PADAP derivative, which is shown as a formula (I); wherein X isHalogen, R 1 And R 2 Each independently selected from C1-C20 alkyl. Compared with the prior art, the method simultaneously introduces the electron-withdrawing group and the large conjugated group into the PADAP to form the PADAP derivative, has obvious color change before and after the combination of the uranyl ions, has higher selectivity, anti-anion and cation competitiveness, cyclability and sensitivity, and can be used as a good ligand for trace amount of uranyl ion recognition in the environment.

Description

PADAP derivative, preparation method and application thereof
Technical Field
The invention belongs to the technical field of analysis, and particularly relates to a PADAP derivative, and a preparation method and application thereof.
Background
As a key component in energy development, nuclear energy has become an important technology in the world to fight against each other. With the advancement of nuclear power engineering, the area of nuclear power development is being continuously expanded. Meanwhile, high attention should be paid to problems such as safety supervision and radiation protection in the processes of construction, production and post-treatment of nuclear power plants. Nuclear accidents caused by improper operations can lead to the global diffusion of nuclear waste through ecosystems such as atmosphere and water, thus bringing great harm to organisms and environment. Therefore, there is a need for a conscious understanding of the severity and necessity of nuclear fuel monitoring and nuclear waste disposal during nuclear power development. The deep development of rapid and specific radionuclide monitoring technology and the application thereof to the detection of practical environmental samples are extremely necessary for the efficient and sensitive prevention and disposal of nuclear accidents and nuclear waste.
At present, detection and analysis technologies based on radionuclide uranium mostly realize uranium detection by modifying or modifying small molecule recognition ligands and combining chemical signal changes generated by uranyl through modified structures. Although some of these methods can achieve better sensitivity or signal transduction capabilities, most of them require expensive instrument characterization or cumbersome sample preparation procedures. Few reports have introduced large conjugated structures to regulate and control colorimetric change before and after ligand binding uranyl, so as to realize detection of high specificity, competitiveness and sensitivity of uranyl.
Meanwhile, the practical application of the ligand-based uranium detection technology has not been widely expanded. So far, most of the literature and patents related to the uranium ligand detection method can only realize uranium detection under laboratory conditions. However, technical researches on the related directions of on-line detection of uranyl in an actual environment sample are rarely reported, and the detection capability of uranyl is poor. For example, chinese patent No. 201710009571.5 discloses a colorimetric identification method for uranyl ions, but it discloses only a colorimetric effect of a compound solution on uranyl ions, and does not investigate the direction of detection of binding of a compound to a material. Chinese patent with application number 201811426845.1 discloses a 2- (5-bromo-2-pyridylazo) -5-diethylaminophenol derivative, a preparation method and application thereof, wherein uranyl is detected by preparing colorimetric test paper and color developing ink, but the detection effect and the detection limit (test paper detection limit: 1 × 10) -5 mol·L -1 ) Weaker and no applied study of trace environmental sample identification was performed. Furthermore, none of the above patents have explored the cyclability of the ligands. Therefore, research on the correlation aspect of reasonably designing a uranium recognition ligand to realize trace uranyl detection in an actual environment is an important problem to be solved in the field of uranium analysis.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a dapp derivative, a preparation method and an application thereof, wherein the dapp derivative has good uranyl ion specificity, anti-anion and cation competition and cyclability.
The invention provides a PADAP derivative, which is shown as a formula (I):
Figure GDA0003936323270000021
wherein X is halogen, R 1 And R 2 Each independently selected from C1-C20 alkyl.
Preferably, said X is Br.
Preferably, said R is 1 And R 2 Is selected from C4-C15 alkyl.
Preferably, said R 1 And R 2 Is selected from C6-C10 alkyl.
Preferably, said R 1 And R 2 Is selected from octyl.
Preferably, the PADAP derivative is as follows:
Figure GDA0003936323270000022
the invention also provides a preparation method of the PADAP derivative, which comprises the following steps:
mixing 3,5-dihalogenated PADAP with a compound shown as a formula (II) for reaction under an anaerobic condition to obtain a PADAP derivative shown as a formula (I);
Figure GDA0003936323270000031
wherein X is halogen, R 1 And R 2 Each independently selected from C1-C20 alkyl.
Preferably, the mixing reaction is carried out in the presence of a catalyst; the catalyst is selected from one or more of tetratriphenylphosphine palladium, palladium acetate, 1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride and bis-triphenylphosphine palladium dichloride.
The invention also provides application of the PADAP derivative as a uranyl ion specific recognition ligand.
The invention also provides colorimetric test paper which comprises the PADAP derivative.
The invention provides a PADAP derivative, which is shown as a formula (I); wherein X is halogen, R 1 And R 2 Each independently selected from C1-C20 alkyl. Compared with the prior art, the invention introduces an electron-withdrawing group and a large conjugated group into the PADAP to form the PADAP derivative, and the PADAP derivative is combinedObvious color change appears before and after the uranyl ions, and the uranyl ions have high selectivity, anti-anion and cation competition, cyclability and sensitivity, and can be used as a good ligand for trace amount uranyl ion identification in the environment.
Experiments show that the detection line of the prepared PADAP derivative shown in the formula (W1) for uranyl ions is 9.33 nanomole; the detection limit of the colorimetric test paper prepared by the invention is 1 multiplied by 10 -8 mol·L -1 。
Drawings
FIG. 1 is a schematic diagram of a process for producing a PADAP derivative represented by the formula (W1) in example 1 of the present invention;
FIG. 2 is a graph of the UV spectrum (FIG. 2 a), the visual colorimetric test chart (FIG. 2 b), the UV spectrum (2 c) of the anti-interference property of different cations, and the visual colorimetric test chart (FIG. 2 d) of the anti-interference property of different cations in a mixed system of the PADAP derivative represented by the formula (W1) prepared in example 1 of the present invention;
FIG. 3 is a comparison of the colorimetric/UV interference resistance of the PADAP derivative represented by formula (W1) in example 1 of the present invention against different anions in a mixed solvent system;
fig. 4 is a graph showing a visual colorimetry test chart (fig. 4 a) of the dapp derivative shown in formula (W1) in example 1 of the present invention for uranyl ions with different concentration gradients, an ultraviolet spectrogram (fig. 4 b), and a fitting curve (fig. 4 c) after detection of uranyl ions with different concentration gradients;
FIG. 5 is a UV spectrum chart of a cyclic test of the PADAP derivative represented by the formula (W1) in a mixed solvent system (FIG. 5 a) and a UV spectrum chart of a cyclic test of the PADAP derivative represented by the formula (W1) in a mixed solvent system (FIG. 5 b) in example 1 of the present invention;
fig. 6 is a test diagram of colorimetric response of the PADAP derivative represented by formula (W1) in example 1 of the present invention to uranyl ions at different concentrations in an actual environmental sample in a mixed solvent system;
fig. 7 is a colorimetric response test chart of the colorimetric test paper prepared in example 2 of the present invention for uranyl ions with different concentrations in an actual environmental sample;
FIG. 8 is a visual colorimetry of the precursors 3,5-2Br-PADAP and the PADAP derivatives represented by the formula (W1) before and after binding to uranyl ions;
FIG. 9 is a diagram showing ultraviolet absorption spectra before and after the precursors 3,5-2Br-PADAP and the uranyl ion binding of the PADAP derivative represented by the formula (W1).
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a PADAP derivative, which is shown as a formula (I):
Figure GDA0003936323270000041
wherein, X is halogen, preferably Br; r is 1 And R 2 Each independently is a C1-C20 alkyl group, preferably a C4-C15 alkyl group, more preferably a C6-C12 alkyl group, even more preferably a C6-C10 alkyl group, and most preferably an octyl group.
In the present invention, the PADAP derivative is most preferably as follows:
Figure GDA0003936323270000051
according to the invention, an electron-withdrawing group and a large conjugated group are simultaneously introduced into the PADAP to form the PADAP derivative, the PADAP derivative shows obvious color change before and after the uranyl ions are combined, has higher selectivity, anti-anion and cation competition, cyclability and sensitivity, and can be used as a good ligand for trace amount uranyl ion identification in the environment.
The invention also provides a preparation method of the PADAP derivative, which comprises the following steps: mixing 3,5-dihalogenated PADAP with a compound shown in a formula (II) for reaction under an anaerobic condition to obtain a PADAP derivative shown in a formula (I);
Figure GDA0003936323270000052
wherein X is halogen, R 1 And R 2 Each independently selected from C1-C20 alkyl; the X, R 1 And R 2 Are the same as above, and are not described herein again.
The invention has no special limitation on the sources of all raw materials, and the raw materials can be prepared by self or sold in the market.
According to the invention, the 3,5-dihalogenated PADAP is preferably prepared according to the following method: heating 3,5-dihalogen-2-aminopyridine and sodium metal in an alcohol solvent for reaction, cooling, adding isoamyl nitrite, and heating for reaction to obtain diazonium salt; reacting the diazonium salt with m-diethylaminophenol under acidic conditions to obtain 3,5-dihalogenated PADAP; the acidic condition is preferably provided by introducing carbon dioxide; the pH value of the acidic condition is preferably 5 to 6.
The compound represented by the formula (II) is preferably prepared according to the following method: heating and reacting a compound shown as a formula (III), pinacol diboron, potassium acetate and a catalyst under an oxygen-free condition to obtain a compound shown as a formula (II); the molar ratio of the compound represented by the formula (III) to the pinacol diboron is preferably 1: (2 to 2.4), more preferably 1:2.2; the compound represented by the formula (III) and potassium acetate are preferably 1: (3 to 3.2), more preferably 1:3.1; the catalyst is preferably a metal palladium catalyst, more preferably an organic palladium catalyst, and is preferably one or more of tetratriphenylphosphine palladium, palladium acetate, 1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride and bistriphenylphosphine palladium dichloride; the mole number of the catalyst is preferably 2 to 5 percent of that of the compound shown in the formula (III), and more preferably 3 to 4 percent; the reaction is preferably carried out in an organic solvent; the organic solvent is preferably 1,4-dioxane; the temperature of the heating reaction is preferably 100-130 ℃, and more preferably 110-120 ℃; the heating reaction time is preferably 12-24 h; after the reaction is finished, preferably cooling to room temperature, adding water for quenching, extracting with dichloromethane, drying an organic layer, filtering and evaporating a solvent, and performing silica gel column chromatography to obtain a compound shown in the formula (II); the eluent for silica gel column chromatography is preferably a mixed solution of ethyl acetate and dichloromethane; the volume ratio of ethyl acetate to dichloromethane is preferably 3:1.
Figure GDA0003936323270000061
mixing 3,5-dihalogenated PADAP with a compound shown as a formula (II) for reaction under an anaerobic condition to obtain a PADAP derivative shown as a formula (I); the reaction is preferably carried out in the presence of a catalyst; the catalyst is preferably an organic palladium catalyst, and more preferably one or more of tetratriphenylphosphine palladium, palladium acetate, 1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride and bistriphenylphosphine palladium dichloride; the reaction is preferably carried out in an organic solvent; the organic solvent is preferably tetrahydrofuran; the reaction is preferably carried out with the addition of an alkaline solution; the alkaline solution is preferably potassium carbonate and/or sodium carbonate solution; the concentration of the alkaline solution is preferably 1 to 3mol/L, and more preferably 2mol/L; the mole number of the alkaline substance in the alkaline solution is preferably 0.2 to 0.8 percent of the mole number of 3,5-dihalogenated PADAP, and more preferably 0.4 to 0.6 percent; the temperature of the mixing reaction is preferably 80-100 ℃, and more preferably 90 ℃; the time of the mixing reaction is preferably 2 to 4 days, and more preferably 3 days; after the reaction is finished, removing the solvent, extracting with dichloromethane and aqueous solution, collecting an organic phase, drying with anhydrous sodium sulfate, adding methanol to precipitate a solid, filtering, and passing filter residue through a column by using a mixed solution of ethyl acetate and petroleum ether to obtain the PADAP derivative shown in the formula (I).
The invention also provides application of the PADAP derivative shown as the formula (I) as a specific uranyl ion recognition ligand. The PADAP derivative shown in the formula (I) is preferably applied to detection of low-concentration uranyl in environmental samples around a tailing pond as a ligand, and has a good effect.
The invention also provides colorimetric test paper which comprises the PADAP derivative shown in the formula (I).
The invention also provides a preparation method of the colorimetric test paper, which comprises the following steps: mixing a PADAP derivative shown in a formula (I) with an organic solvent to obtain a PADAP derivative solution; soaking the filter paper in a PADAP derivative solution, and drying to obtain colorimetric test paper; the filter paper is preferably quick filter paper; the soaking time is preferably 20-60 min, more preferably 20-40 min, and still more preferably 30min; the drying is preferably vacuum drying.
The colorimetric detection test paper prepared by the invention can quickly and sensitively monitor trace uranyl in an environmental sample. The establishment of the analysis method provides a better application idea for detecting trace uranyl ions in the environment.
In order to further illustrate the present invention, the following will describe in detail a PADAP derivative, its preparation method and application.
The reagents used in the following examples are all commercially available.
Example 1
The preparation of the PADAP derivative of the formula (W1) according to the preparation scheme shown in FIG. 1
1.1 preparation of intermediate 3,5-dibromo-2-azopyridine salt
0.04mol (10.08 g) 3,5-dibromo-2-aminopyridine was dissolved in 40ml of absolute ethanol, 2g of metallic sodium was dissolved in 60ml of absolute ethanol, mixed and charged into a round-bottomed flask. Condensing and refluxing for half an hour, cooling, adding 10ml of newly prepared isoamyl nitrite, stirring and refluxing for 2 hours at 65-75 ℃, cooling, separating out solid, performing suction filtration, and performing vacuum drying to obtain bright yellow powder, namely the diazonium salt.
1.2 preparation of intermediate 3,5-dibromo-PADAP
10mmol (3.02 g) of the diazonium salt prepared in 1.1 are taken up in 20ml of ethanol +4ml of water and 11mmol (1.82 g) of m-diethylaminophenol are taken up in 20ml of absolute ethanol, mixed and passed through with carbon dioxide at room temperature for 0.5h, the pH is adjusted to weak acidity (approximately between 5 and 6), the reaction is continued for 4h and left overnight. After the solution was spun to 4-5 ml, 30ml of water was added to precipitate out a precipitate, which was filtered and washed with hot water several times. The crude product was passed through a column of ethyl acetate/petroleum ether =3:1 and the solution was spin dried and vacuum dried to give dark red needle crystals.
1.3 preparation of the intermediate 9,9-dioctylfluorene-2,7-pinacol ester diborate
9,9-dioctyl-2,7-dibromofluorene (1.000g, 2.04mmol), pinacol diboron (1.140g, 4.49mmol), potassium acetate (1.262g, 6.41mmol) and 1,1' -bis diphenylphosphine ferrocene palladium dichloride (abbreviated as PdCl) 2 dppf) (92.4 mg, 0.063mmol) was placed in a 250mL two-neck round bottom flask. The flask was evacuated and flushed with dry nitrogen three times. The flask was then charged with anhydrous 1,4-dioxane (40 mL). The reaction mixture was heated to 110 ℃ and refluxed overnight. After the reaction, the solution was cooled to room temperature, quenched with water, extracted with dichloromethane, and the organic layers were combined and dried over magnesium sulfate. The solvent was filtered and evaporated, and the crude product was purified by silica gel column chromatography using ethyl acetate/dichloromethane mixture (3/1 by volume) as eluent to give a white powder.
1.4 preparation of PADAP derivative represented by the formula (W1)
0.426g (1 mmol) of 3,5-dibromo-PADAP obtained in 1.2, 0.643g (1 mmol) of 9,9-dioctylfluorene-2,7-pinacol diboronate obtained in 1.3, and 0.058g (0.05 mmol) of tetrakis (triphenylphosphine) palladium (abbreviated as Pd (PPh) 3 ) 4 ) Dissolved in 5ml of Tetrahydrofuran (THF) and introduced into a sealed tube, followed by addition of 2mL of 2.0 mol. L -1 Potassium carbonate (K) 2 CO 3 ) And (4) vacuumizing the sealed tube, introducing nitrogen, and performing the process three times. The reaction was stirred at 90 ℃ for 3 days. After the solvent was spin-dried, the organic phase was collected by extraction with dichloromethane/water, dried over anhydrous sodium sulfate, the solution was added to 100ml of methanol, and the solid was precipitated and filtered off. And (3) filtering the filter residue by using ethyl acetate/petroleum ether =3:1 to pass through a column, and spin-drying to obtain orange-red powder.
1.5 preparation of a PADAP derivative Standard solution represented by the formula (W1):
the PADAP derivative represented by the above formula (W1) was dissolved in tetrahydrofuran to prepare 1X 10 -3 mol·L -1 And (4) storing the standard solution at room temperature in a dark place, and diluting to the required scale when in use.
1.6 colorimetric/UV specificity and competitive identification (cation) of PADAP derivative Standard solution represented by formula (W1)
Specific recognition: a PADAP derivative standard solution represented by the formula (W1) prepared at 1.5 was dissolved in a mixed solvent (THF: H) 2 O =1:1, the same applies below) after dilution (100-fold dilution to 1 × 10 -5 mol·L -1 Solution), adding the cationic solution (UO) to be tested respectively 2 2+ ,Cu 2+ ,Co 2+ ,Ni 2+ ,Cd 2+ ,Zn 2+ ,Pb 2+ ,Ba 2+ ,Al 3+ ,Cr 3+ ,Fe 3+ ,Zr 4+ ,Dy 3+ ,La 3+ ,Eu 3+ ,Sm 3+ ,Th 4+ ,Mg 2+ ,Hg 2+ Ca 2+ ,Bi 3+ ,Ag + ,K + ,Na + ) To obtain a mixed solution to be measured (the concentration of the cation in the mixed solution and the molar concentration of W1 are both 1X 10) -5 mol·L -1 ) After shaking the mixed solution to be tested, placing the mixed solution under natural light for 10 minutes, and directly carrying out visual colorimetric test, as shown in fig. 2 b; then the solution was transferred to a cuvette and tested for uv spectroscopy, resulting in a uv spectrum as shown in figure 2 a.
Competitive identification: a PADAP derivative standard solution represented by the formula (W1) prepared at 1.5 was diluted (100-fold to 1X 10-fold) with a mixed solvent -5 mol·L -1 Solution), adding uranyl ions with the same quantity as W1, and then respectively adding a cation solution (Cu) to be detected 2+ ,Co 2+ ,Ni 2+ ,Cd 2+ ,Zn 2+ ,Pb 2+ ,Ba 2+ ,Al 3+ ,Cr 3+ ,Fe 3+ ,Zr 4+ ,Dy 3+ ,La 3+ ,Eu 3+ ,Sm 3+ ,Th 4 + ,Mg 2+ ,Hg 2+ Ca 2+ ,Bi 3+ ,Ag + ,K + ,Na + ) To obtain a mixed solution to be tested (the concentration of the cations in the mixed solution and the molar concentration of W1 are both 1X 10) -5 mol·L -1 ) After shaking the mixed solution to be tested, placing the mixed solution under natural light for 10 minutes, and directly carrying out visual colorimetric test, as shown in fig. 2 d; then transferring the solution into a cuvette for ultraviolet spectrum test to obtain ultravioletThe spectrum is shown in figure 2 c.
1.7 colorimetric/UV competitive identification (anion) of PADAP derivative standard solutions represented by the formula (W1):
a PADAP derivative standard solution represented by the formula (W1) prepared at 1.5 was diluted (100-fold to 1X 10-fold) with a mixed solvent -5 mol·L -1 Solution), uranyl ions equivalent to the PADAP derivative represented by formula (W1) were added, and then anion solutions to be measured (HCO) were added, respectively 3 - ,SO 4 3- ,Cl - ,SO 3 2- ,CO 3 2- ,Ac - ,Br - ,HSO 3 - ,PO 4 3- ,NO 2 - ) To obtain a mixed solution to be measured (the concentration of the anions in the mixed solution and the molar concentration of W1 are both 1X 10) -5 mol·L -1 ) After shaking the mixed solution to be tested, placing the mixed solution under natural light for 10 minutes, and directly carrying out visual colorimetric test; and then transferring the solution to a cuvette for ultraviolet spectrum test to obtain a colorimetric/ultraviolet anti-interference contrast diagram of the PADAP derivative shown as the formula (W1) on different anions in a mixed solvent system, wherein the colorimetric/ultraviolet anti-interference contrast diagram is shown as a figure 3.
1.8 determining the naked eye colorimetric/ultraviolet detection limit of the PADAP derivative standard solution shown as the formula (W1):
the PADAP derivative standard solution represented by the formula (W1) prepared at 1.5 was diluted (100-fold to 1X 10-fold) with a mixed solvent -5 mol·L -1 Solution), adding uranyl ion solutions with different concentrations respectively to obtain mixed solution to be measured (the concentration of the uranyl ions in the mixed solution and the molar concentration of W1 are both 1 × 10 -5 mol·L -1 ) After shaking the mixed solution to be tested, placing the mixed solution under natural light for 10 minutes, and directly carrying out visual colorimetric test, as shown in fig. 4 a; the naked eye colorimetric detection limit of the obtained PADAP derivative shown as the formula (W1) on uranyl ions is 5 multiplied by 10 -7 mol·L -1 (ii) a The solution was then transferred to a cuvette for uv spectroscopy as shown in figure 4 b; the data were processed to obtain a fitted graph as shown in figure 4 c. Obtaining the purple of the uranium acyl ions of the PADAP derivative shown as the formula (W1) according to the detection limit calculation formula LOD =3 delta/KThe external detection limit is 9.33 multiplied by 10 -9 mol·L -1 9.33 nanomoles.
1.9 measurement of cyclicity of PADAP derivative Standard solution represented by the formula (W1)
(1) The PADAP derivative standard solution represented by the formula (W1) prepared in 1.5 was diluted with a mixed solvent (100-fold dilution to 1X 10) -5 mol·L -1 Solution), adding blank of (a) respectively; (b) an equivalent amount of uranyl ion solution; (c) Equal amount of uranyl ion solution and equal amount of 1,2-dimethyl-3-hydroxy-4-pyridone (HOPO for short) water solution; (d) And (3) oscillating the mixed solution to be tested, placing the mixed solution for 10 minutes, and transferring the mixed solution to a cuvette for ultraviolet spectrum testing, wherein the mixed solution comprises an equivalent uranyl ion solution, an equivalent HOPO aqueous solution and an equivalent uranyl ion solution, and the mixed solution is as shown in figure 5 a.
(2) The PADAP derivative standard solution represented by the formula (W1) prepared in 1.5 was diluted with a mixed solvent (100-fold dilution to 1X 10) -5 mol·L -1 Solution), separately adding: (a) blank; (b) an equal amount of uranyl ion solution; (c) Equal amount of uranyl ion solution and equal amount of 1,2-dimethyl-3-hydroxy-4-pyridone (HOPO for short) water solution; (d) An equivalent uranyl ion solution, an equivalent HOPO aqueous solution and an equivalent uranyl ion solution; (e) Equivalent uranyl ion solution, equivalent HOPO aqueous solution, equivalent uranyl ion solution and equivalent HOPO aqueous solution; (f) … and so on, preparing 11 groups of solutions, shaking all prepared solutions, standing for 10 minutes, and transferring to a cuvette for ultraviolet spectrum test to obtain an ultraviolet spectrum diagram, as shown in fig. 5 b.
The cyclability is that the ligand can not be competed by another ligand which is more excellent in combination with uranium after being combined with uranyl ions to form a complex, so that the ligand can be detected again. 1,2-dimethyl-3-hydroxy-4-pyridone (HOPO for short) is used as a competitor for the dapp derivative of formula (W1) in the present invention because HOPO is an excellent uranium excretion promoter with a binding constant for uranyl ions much greater than that of other ligands. Therefore, when the dapp derivative represented by the formula (W1) binds to uranyl ions, cyclic detection of the dapp derivative represented by the formula (W1) is performed by adding an equal amount of HOPO as a competitor. It was found that the addition of HOPO resulted in the reappearance of the characteristic dapp derivative ligand peak (508 nm) of formula (W1), while the 625nm characteristic peak of the dapp derivative-uranyl complex of formula (W1) was reduced, thereby completing the one-cycle process (as shown in fig. 5 a). The padp derivative represented by formula (W1) can be repeatedly cycled five times, and the cycling efficiency remains above 80% (as shown in fig. 5 b), demonstrating that the padp derivative represented by formula (W1) has good cycling detection capability.
1.10 environmental sample detection application of a PADAP derivative standard solution represented by the formula (W1):
(1) According to the requirements of the international standardization organization standard (ISO 5667-14-1998 part 14 of water quality sampling), surface water surface layer water samples around a 272 uranium ore tailing pond are collected on site, and the water samples are filtered for three times through slow qualitative filter paper (aperture: 1-3 μm) and stored in a dark place for later use.
(2) The uranyl ion solutions with different concentrations are prepared by adopting an environment water sample in 1.10 (1), and are respectively configured with a concentration gradient of 1 multiplied by 10 -5 mol·L -1 ，8×10 -6 mol·L -1 ，6×10 -6 mol·L -1 ，4×10 -6 mol·L -1 ，2×10 -6 mol·L -1 ，1×10 -6 ，5×10 -7 mol·L -1 The uranyl ion solution is ready for use.
(3) The PADAP derivative standard solution shown in the formula (W1) prepared in 1.5 is mixed with a solvent (THF: H) prepared from an environmental water sample 2 O (environmental water sample) = 1:1) after dilution (100 times to 1 × 10 dilution) -5 mol·L -1 Solution), add the uranyl ion solution of the different concentrations that dispose in 1.10 (1) respectively, obtain the mixed solution that awaits measuring, after shaking the mixed solution that awaits measuring, place behind 10 minutes under the natural light, directly carry out the colorimetric test of visualing, judge the detectability (detection limit) of the solution of W1 configuration to environmental water sample uranium: 1X 10 -6 mol·L -1 ) A visual colorimetric test chart was obtained as shown in fig. 6.
Example 2
2.1 preparation of PADAP derivative dipping colorimetric test paper shown in formula (W1) and detection effect of the PADAP derivative dipping colorimetric test paper on environmental samples:
(1) The solution of uranyl ions with different concentrations adopts the environmental water in 1.10 (1)Preparing samples, respectively configuring the concentration gradient to be 1 multiplied by 10 -4 mol·L -1 ，1×10 -5 mol·L -1 ，1×10 -6 mol·L -1 ，1×10 -7 mol·L -1 ，1×10 -8 mol·L -1 ，5×10 -8 mol·L -1 ，1×10 -9 mol·L -1 The uranyl ion solution is ready for use.
(2) The PADAP derivative standard solution represented by the formula (W1) prepared in 1.5 was diluted (100-fold to 1X 10 times) -5 mol·L -1 Solution), the dried rapid filter paper was immersed in the diluted solution of the PADAP derivative represented by formula (W1), immersed for 30 minutes, taken out, and vacuum-dried to obtain a colorimetric test paper based on the PADAP derivative represented by formula (W1).
(3) Respectively immersing the prepared colorimetric test paper based on the PADAP derivative shown in the formula (W1) into uranyl ion solutions (environmental water samples) with different concentration gradients prepared in 1.10 (1), taking out and airing after 1 minute, carrying out visual colorimetric detection to obtain a visual colorimetric detection image, judging the detection capability and detection limit of the colorimetric test paper prepared from W1 on the uranium in the environmental water sample by using a graph 7 as shown in figure 7, and obtaining the detection limit of 1 multiplied by 10 -8 mol·L -1 。
Example 3 verification of sensitivity of PADAP derivative represented by formula (W1)
The color and corresponding ultraviolet spectrum before and after the precursors 3,5-2Br-PADAP and the PADAP derivatives shown in the formula (W1) are combined with uranyl ions are researched, and a visual colorimetric detection graph is obtained and shown in FIG. 8; the ultraviolet absorption spectrum (inset: 3,5-2Br-PADAP, color change pattern of the PADAP derivative represented by formula (W1) and its uranyl complex) is shown in FIG. 9. From FIGS. 8 and 9, it can be seen that a certain red shift of the maximum ultraviolet absorption peak (455 nm) of PADAP (430 nm) (Florence, T.M.; johnson, D.A.; farrar, Y.J. Anal.Chem.1969,41, 1652-1654.) and 5-Br-PADAP (450 nm) (Wu, X.; mao, Y.; wang, D.; huang, Q.; yin, Q.; ZHEN, M.; hu Q.; wang, H.Sens.Actussors B3236 zx3236. And Johnson, D.A.; florence, T.M.Anal.Chim.acta 1971,53,73), the precursor 3,5-2Br-PADAP occurs, which indicates that the introduction of the maximum absorption wavelength halogen group causes the maximum absorption of the ligandA red shift occurs. Most importantly, the maximum absorption wavelength of the PADAP derivative shown in the formula (W1) prepared by simultaneously introducing the borate group and the electron-withdrawing halogen group generates obvious bathochromic shift (508 nm), which is higher than the bathochromic shift degree (480 nm) of Triphenylamine-PADAP (Chinese patent of 201710009571.5' a colorimetric identification method of uranyl ions) 2 ) Larger, thereby successfully adjusting the solution color from light yellow to red (fig. 8). Meanwhile, the maximum absorption wavelength (625 nm) of the uranyl complex formed after the uranyl ion is combined is more red-shifted than that of Triphenanamine-PADAP (602.5 nm), so that the obvious color change (red → blue, an inset in FIG. 9) before and after the PADAP derivative shown in the formula (W1) is combined with the uranyl ion is realized. In the colorimetric/uv method, this significant color change means that even lower concentrations of uranyl ions can cause a color/luminosity change in W1, which is why the sensitivity of W1 to uranyl can be as low as nanomolar.

Claims (10)

1. A PADAP derivative represented by formula (I):
Figure FDA0002433317620000011
wherein X is halogen, R 1 And R 2 Each independently selected from C1-C20 alkyl.
2. The PADAP derivative of claim 1, wherein X is Br.
3. The PADAP derivative of claim 1, wherein R is 1 And R 2 Is selected from C4-C15 alkyl.
4. The PADAP derivative of claim 1, wherein R is 1 And R 2 Is selected from C6-C10 alkyl.
5. The PADAP derivative according to claim 1,wherein R is 1 And R 2 Selected from octyl.
6. The PADAP derivative of claim 1, wherein the PADAP derivative is represented by:
Figure FDA0002433317620000012
7. a method for preparing a dapp derivative, comprising:
mixing 3,5-dihalogenated PADAP with a compound shown in a formula (II) for reaction under an anaerobic condition to obtain a PADAP derivative shown in a formula (I);
Figure FDA0002433317620000013
Figure FDA0002433317620000021
wherein X is halogen, R 1 And R 2 Each independently selected from C1-C20 alkyl.
8. The production method according to claim 7, wherein the mixing reaction is carried out in the presence of a catalyst; the catalyst is selected from one or more of palladium tetratriphenylphosphine, palladium acetate, 1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride and palladium bistriphenylphosphine dichloride.
9. Use of the PADAP derivative according to any of claims 1 to 6 as a uranyl ion-specific recognition ligand.
10. A colorimetric test paper comprising the PADAP derivative according to any one of claims 1 to 6.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106802298A (en) * 2017-01-06 2017-06-06 中国工程物理研究院核物理与化学研究所 A kind of colorimetric recognition methods of uranyl ion
CN109456260A (en) * 2018-11-27 2019-03-12 南华大学 2- (5- Bromo-2-pyridylazo) -5- lignocaine amphyl, preparation method and application
CN110294837A (en) * 2019-07-05 2019-10-01 南华大学 A kind of amidoxim fluidized polymer, preparation method and application
CN110715922A (en) * 2019-11-20 2020-01-21 福州大学 Br-PADAP-uranyl ion spectrophotometry

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106802298A (en) * 2017-01-06 2017-06-06 中国工程物理研究院核物理与化学研究所 A kind of colorimetric recognition methods of uranyl ion
CN109456260A (en) * 2018-11-27 2019-03-12 南华大学 2- (5- Bromo-2-pyridylazo) -5- lignocaine amphyl, preparation method and application
CN110294837A (en) * 2019-07-05 2019-10-01 南华大学 A kind of amidoxim fluidized polymer, preparation method and application
CN110715922A (en) * 2019-11-20 2020-01-21 福州大学 Br-PADAP-uranyl ion spectrophotometry

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