CN111303193A - PADAP derivative, preparation method and application thereof - Google Patents

PADAP derivative, preparation method and application thereof Download PDF

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CN111303193A
CN111303193A CN202010243455.1A CN202010243455A CN111303193A CN 111303193 A CN111303193 A CN 111303193A CN 202010243455 A CN202010243455 A CN 202010243455A CN 111303193 A CN111303193 A CN 111303193A
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padap
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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 is halogen, R1And R2Each independently selected from C1-C20 alkyl. Compared with the prior art, the invention introduces the electron-withdrawing group and the large conjugated group 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.

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 application No. 201710009571.5 discloses a colorimetric identification method of uranyl ions, but it only discloses a colorimetric effect of a compound solution on uranyl ions, and does not investigate the direction in which the binding of a compound to a material is detected. Chinese patent application No. 201811426845.1 discloses 2- (5-bromo-2-pyridylazo) -5-diethylaminophenol derivatives, 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)-5mol·L-1) Is weaker and does not proceedApplication research of trace environment sample identification. 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 BDA0002433317630000021
wherein X is halogen, R1And R2Each independently selected from C1-C20 alkyl.
Preferably, said X is Br.
Preferably, said R is1And R2Is selected from alkyl of C4-C15.
Preferably, said R is1And R2Is selected from alkyl of C6-C10.
Preferably, said R is1And R2Is selected from octyl.
Preferably, the PADAP derivatives are as follows:
Figure BDA0002433317630000022
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 BDA0002433317630000031
wherein X is halogen, R1And R2Each 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' -bis (diphenylphosphino) ferrocene ] palladium dichloride and bis-triphenylphosphine palladium dichloride.
The invention also provides application of the PADAP derivative as a specific uranyl ion recognition ligand.
The invention also provides a 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, R1And R2Each independently selected from C1-C20 alkyl. Compared with the prior art, the invention introduces the electron-withdrawing group and the large conjugated group 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.
Experiments show that the detection line of the uranium acyl ions by the PADAP derivative shown in the formula (W1) prepared by the invention is 9.33 nanomole; the detection limit of the colorimetric test paper prepared by the invention is 1 multiplied by 10-8mol·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. 2a), the visual colorimetric test chart (FIG. 2b), the UV spectrum (2c) of the anti-interference performance of different cations, and the visual colorimetric test chart (FIG. 2d) of the anti-interference performance 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 PADAP derivatives of formula (W1) in a mixed solvent system for different anions in example 1 of the present invention;
fig. 4 is a graph (fig. 4a) of a visual colorimetry test chart (fig. 4a) of the dapp derivative shown in formula (W1) for uranyl ions with different concentration gradients, an ultraviolet spectrogram (fig. 4b) and a fitting curve (fig. 4c) of the dapp derivative after detection of uranyl ions with different concentration gradients in example 1 of the present invention;
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. 5a) and a UV spectrum chart of a cyclic test of the PADAP derivative represented by the formula (W1) in a mixed solvent system (FIG. 5b) in example 1 of the present invention;
fig. 6 is a test chart of colorimetric response of the dapp derivative represented by the 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 a derivative of formula (W1) before and after binding to uranyl ions;
FIG. 9 is a graph showing ultraviolet absorption spectra before and after the precursors 3,5-2Br-PADAP and the uranyl ion binding reaction 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 BDA0002433317630000041
wherein, X is halogen, preferably Br; r1And R2Each independently is a C1-C20 alkyl group, preferably a C4-C15 alkyl group, more preferably a CIs C6-C12 alkyl, more preferably C6-C10 alkyl, and most preferably octyl.
In the present invention, the PADAP derivative is most preferably as follows:
Figure BDA0002433317630000051
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 as a formula (II) for reaction under an anaerobic condition to obtain a PADAP derivative shown as a formula (I);
Figure BDA0002433317630000052
wherein X is halogen, R1And R2Each independently selected from C1-C20 alkyl; the X, R1And R2Are 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 metal sodium 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-dihalogeno-PADAP; the acidic condition is preferably provided by introducing carbon dioxide; the pH value of the acidic condition is preferably 5-6.
The compound represented by the formula (II) is preferably prepared by 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 further preferably one or more of palladium tetratriphenylphosphine, palladium acetate, 1' -bis (diphenylphosphino) ferrocene ] palladium dichloride and palladium bistriphenylphosphine 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 BDA0002433317630000061
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' -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 1-3 mol/L, and more preferably 2 mol/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 the 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 mixing reaction time is preferably 2-4 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 a 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 a quick filter paper; the soaking time is preferably 20-60 min, more preferably 20-40 min, and further preferably 30 min; 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 PADAP derivative represented by the formula (W1) was prepared according to the preparation scheme shown in FIG. 1
1.1 preparation of 3, 5-dibromo-2-azopyridine salt as intermediate
0.04mol (10.08g) of 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. And (3) cooling after condensing and refluxing for half an hour, adding 10ml of newly prepared isoamyl nitrite, stirring and refluxing for 2 hours at 65-75 ℃, cooling, separating out a 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
Dissolving 10mmol (3.02g) of the diazonium salt prepared in 1.1 in 20ml of ethanol +4ml of water, dissolving 11mmol (1.82g) of m-diethylaminophenol in 20ml of absolute ethanol, mixing, introducing carbon dioxide at room temperature for 0.5h, adjusting the pH value to weak acidity (about between 5 and 6), continuing to react for 4h, and standing overnight. And (3) spinning the solution to 4-5 ml, adding 30ml of water to precipitate out a precipitate, filtering the precipitate, and washing the precipitate with hot water for multiple times. The crude product is passed through a column with ethyl acetate/petroleum ether being 3:1, the solution is dried by spinning and then dried in vacuum, and dark red needle-shaped crystals are obtained.
1.3 preparation of intermediate 9, 9-dioctylfluorene-2, 7-diboronic acid pinacol ester
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-diphenylphosphino ferrocene palladium dichloride (PdCl for short)2dppf) (92.4mg, 0.063mmol) was placed in a 250mL two-neck round bottom flask. The flask was evacuated and flushed with dry nitrogen three times. Anhydrous 1, 4-dioxane (40mL) was then added to the flask. 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. Filtration and evaporation of the solvent purified the crude product by silica gel column chromatography using ethyl acetate/dichloromethane mixture (3/1 vol/vol) as eluent to give a white powder.
1.4 preparation of PADAP derivative represented by the formula (W1)
0.426g (1mmol) of 3, 5-dibromo-PADAP obtained in 1.2, 0.643g (1mmol) of 9, 9-dioctylfluorene-2, 7-diboronic acid pinacol ester obtained in 1.3, 0.058g (0.05mmol) of tetrakis (triphenylphosphine) palladium (abbreviated as Pd (PPh)3)4) Dissolved in 5mL of Tetrahydrofuran (THF) and added to a sealed tube, followed by 2mL of 2.0 mol. L-1Potassium carbonate (K)2CO3) 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 (4) filtering filter residues by using ethyl acetate/petroleum ether at a ratio of 3:1, and performing spin drying to obtain orange red powder.
1.5 preparation of a standard solution of a PADAP derivative represented by the formula (W1):
the PADAP derivative represented by the above formula (W1) was dissolved in tetrahydrofuran to prepare a solution of 1X 10-3mol·L-1And (5) storing the standard solution at room temperature in the dark, 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)2O1: 1, the same applies below) diluted (100-fold to 1 × 10 dilution)-5mol·L-1Solution), adding the cationic solution (UO) to be tested respectively2 2+,Cu2+,Co2+,Ni2+,Cd2+,Zn2+,Pb2+,Ba2+,Al3+,Cr3+,Fe3+,Zr4+,Dy3+,La3+,Eu3+,Sm3+,Th4+,Mg2+,Hg2+Ca2+,Bi3+,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 10-5mol·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: the PADAP derivative standard solution shown in formula (W1) and prepared at 1.5 is diluted with a mixed solventRelease (100-fold dilution to 1X 10)-5mol·L-1Solution), adding uranyl ions with the same amount as W1, and adding to-be-detected cation solution (Cu)2+,Co2+,Ni2+,Cd2+,Zn2+,Pb2+,Ba2+,Al3+,Cr3+,Fe3+,Zr4+,Dy3+,La3+,Eu3+,Sm3+,Th4 +,Mg2+,Hg2+Ca2+,Bi3+,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 10-5mol·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; the solution was then transferred to a cuvette and tested for uv spectroscopy, resulting in a uv spectrum as shown in figure 2 c.
1.7 colorimetric/UV competitive identification (anion) of PADAP derivative standard solutions of 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 the mixed solvent-5mol·L-1Solution), uranyl ions equivalent to the padpa derivative represented by the formula (W1) were added, and then anion solutions to be measured (HCO) were added respectively3 -,SO4 3-,Cl-,SO3 2-,CO3 2-,Ac-,Br-,HSO3 -,PO4 3-,NO2 -) To obtain a mixed solution to be tested (the concentration of the anions in the mixed solution and the molar concentration of W1 are both 1 × 10-5mol·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; then the solution is transferred to a cuvette and subjected to ultraviolet spectrum test, and a colorimetric/ultraviolet interference resistance comparison graph of the PADAP derivative shown as the formula (W1) on different anions in a mixed solvent system is obtained, as shown in FIG. 3.
1.8 determination of naked eye colorimetric/ultraviolet detection limit of PADAP derivative standard solution represented by 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-5mol·L-1Solution), 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 × 10-5mol·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 limit of naked-eye colorimetric detection of uranyl ions by the obtained PADAP derivative represented by the formula (W1) is 5 × 10-7mol·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 fit a graph as shown in figure 4 c. The ultraviolet detection limit of uranyl ions of the dapp derivative represented by formula (W1) was 9.33 × 10 according to the detection limit calculation formula LOD 3 δ/K-9mol·L-19.33 nanomoles.
1.9 measurement of the cyclicity of the 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)-5mol·L-1Solution), adding blank of (a) respectively; (b) equivalent 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)-5mol·L-1Solution), separately adding: (a) blank; (b) equivalent 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) an equivalent uranyl ion solution, an equivalent HOPO aqueous solution, an equivalent uranyl ion solution and an equivalent HOPO aqueous solution; (f) … toAnd similarly, preparing 11 groups of solutions, shaking all the prepared solutions, standing for 10 minutes, and transferring to a cuvette for ultraviolet spectrum test to obtain an ultraviolet spectrum chart, 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. In the present invention, 1, 2-dimethyl-3-hydroxy-4-pyridone (HOPO for short) is used as a competitor for the dapp derivative represented by formula (W1), because HOPO is an excellent uranium excretion promoter whose binding constant to uranyl ions is much greater than that of other ligands. Therefore, when the dapp derivative represented by the formula (W1) binds to a uranyl ion, 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 PADAP derivative ligand peak (508nm) of formula (W1), while the reduction of the characteristic PADAP derivative-uranyl complex 625nm peak of formula (W1) resulted in the completion of one cycle (as shown in FIG. 5 a). The padp derivative represented by formula (W1) can be cycled five times, and the cycling efficiency remains above 80% (as shown in fig. 5b), demonstrating that the padp derivative represented by formula (W1) has good cycling detection ability.
1.10 environmental sample detection applications of PADAP derivative standard solutions represented by 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 surface 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 10-5mol·L-1，8×10-6mol·L-1，6×10-6mol·L-1，4×10-6mol·L-1，2×10-6mol·L-1，1×10-6，5×10-7mol·L-1The uranyl ion solution is ready for use.
(3) The PADAP derivative standard solution shown in formula (W1) prepared in 1.5 is mixed with a solvent prepared from an environmental water sample (THF: H)2Diluting O (environmental water sample) to 1:1 (100 times to 1 × 10)-5mol·L-1Solution), 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 10-6mol·L-1) A visual colorimetric test chart was obtained as shown in fig. 6.
Example 2
2.1 preparation of PADAP derivative-impregnated colorimetric test paper represented by formula (W1) and its effect on environmental sample detection:
(1) 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 10-4mol·L-1，1×10-5mol·L-1，1×10-6mol·L-1，1×10-7mol·L-1，1×10-8mol·L-1，5×10-8mol·L-1，1×10-9mol·L-1The 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)-5mol·L-1Solution), the dried quick filter paper was immersed in the diluted solution of the dapp derivative represented by formula (W1), immersed for 30 minutes, taken out, and vacuum-dried to obtain a colorimetric test paper based on the dapp 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 chart, and judging the detection capacity and detection limit of the colorimetric test paper prepared from W1 on the environmental water sample uranium by using the chart 7 as shown in FIG. 7 to obtain the detection limit of 1 multiplied by 10-8mol·L-1。
Example 3 verification of sensitivity of PADAP derivative represented by formula (W1)
The colors and corresponding ultraviolet spectrums 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 of PADAP derivative represented by formula (W1) and uranyl complex thereof) is shown in FIG. 9. It can be seen from FIGS. 8 and 9 that the maximum ultraviolet absorption peak (455nm) of the precursor 3,5-2Br-PADAP is bathed by the introduction of electron-withdrawing halogen groups, which indicates that the introduction of electron-withdrawing halogen groups can red-shift the maximum absorption wavelength of the ligand, relative to PADAP (430nm) (Florence, T.M.; Johnson, D.A.; Farrar, Y.J. Anal.Chem.1969,41, 1652-. 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 is significantly red-shifted (508nm), which is higher than the red-shifted degree (480 nm) of Triphenylamine-PADAP (Chinese patent with application number 201710009571.5, a colorimetric identification method for uranyl ions)2) Larger, thereby successfully adjusting the solution color from light yellow to red (fig. 8). Meanwhile, the maximum absorption wavelength (625nm) of the uranyl complex formed after the uranyl ion is combined is more redshifted than that of Triphenanamine-PADAP (602.5nm), so that the obvious color change before and after the PADAP derivative shown in the formula (W1) is combined with the uranyl ion (red → blue, and an inset in FIG. 9) 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, R1And R2Each 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 is1And R2Is selected from alkyl of C4-C15.
4. The PADAP derivative of claim 1, wherein R is1And R2Is selected from alkyl of C6-C10.
5. The PADAP derivative of claim 1, wherein R is1And R2Is selected from octyl.
6. The PADAP derivative of claim 1, wherein the PADAP derivative is as follows:
Figure FDA0002433317620000012
7. a method for preparing a dapp derivative, comprising:
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 FDA0002433317620000013
Figure FDA0002433317620000021
wherein X is halogen, R1And R2Each 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 tetratriphenylphosphine palladium, palladium acetate, 1' -bis (diphenylphosphino) ferrocene ] palladium dichloride and bis-triphenylphosphine palladium dichloride.
9. Use of the PADAP derivative according to any one 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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