CN108623538B - Piperazine modified tetraphenylethylene derivative and application thereof - Google Patents
Piperazine modified tetraphenylethylene derivative and application thereof Download PDFInfo
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Abstract
The invention discloses a piperazine modified tetraphenylethylene derivative, the structural formula of which is shown as formula I, and also discloses a preparation method of the piperazine modified tetraphenylethylene derivative, wherein 1- (4 '-bromophenyl) -1,2, 2-triphenylethylene and 4- (4' -carbonate-1-piperazinyl) phenylboronic acid pinacol ester are coupled through a Suzuki reaction, and the piperazine modified tetraphenylethylene derivative is finally obtained through separation and purification treatment such as concentration, extraction, drying, column chromatography and the like‑6M level.
Description
Technical Field
The invention belongs to the technical field of organic photoelectric functional materials, and particularly relates to a piperazine modified tetraphenylethylene derivative and application thereof, in particular to application in detection of 2,4, 6-Trinitrophenol (TNP) as an aromatic nitro explosive.
Background
The nitro-aromatic hydrocarbons including Nitrobenzene (NB), 4-nitrotoluene (4-NT), 2,4, 6-Trinitrophenol (TNP), 2,4, 6-trinitrotoluene (TNT) and the like are common components of explosives, and have stronger explosive capacity and lower safety coefficient. At present, nitro compounds are concerned greatly in aspects of national safety, environmental pollution and the like, so that the detection of the nitro compounds is particularly important.
The detection technology of the aromatic nitro explosives developed at present comprises mass spectrometry, ion mobility spectrometry, an electrochemical method, a colorimetric method and the like, but the conventional detection and analysis methods have the defects of low sensitivity, general selectivity effect or long detection response time and the like.
In addition, 2,4, 6-Trinitrophenol (TNP) among nitroaromatics is a very dangerous chemical substance that can explode violently when it comes into contact with flames or is subjected to frictional impact. Moreover, the ingestion of TNP can cause poisoning of the body, with mild cases having symptoms such as headache, nausea, vomiting, abdominal pain, etc., and severe cases causing damage to the erythrocytes. However, all nitro explosives show strong electron affinity, and it is difficult to specifically detect TNP from other nitro compounds, so it is important to develop a method for highly efficient and specific detection of TNP.
Since 2001, the aggregation-induced emission (AIE) phenomenon was discovered by the task group of tang, the application of fluorescent materials with AIE properties in the fields of chemical and biological detection has become a focus of recent research, and the fluorescent detection of explosives using AIE materials has also received great attention. This is because, on the one hand, the fluorescence detection method has the advantages of high sensitivity, high selectivity and short response time compared with the conventional explosion detection analysis method; on the other hand, the AIE material can keep high-efficiency fluorescence under high concentration and aggregation state, and is helpful for further improving detection sensitivity.
Disclosure of Invention
The invention aims to provide a piperazine modified tetraphenylethylene derivative which is used as a fluorescent probe molecule for detecting aromatic nitro explosives, and the fluorescent detection method has high sensitivity, strong selectivity and short response time; and can specifically detect TNP.
A piperazine modified tetraphenylethylene derivative has a structural formula shown in formula I:
wherein R is alkyl.
Preferably, R is methyl, ethyl, propyl, isopropyl, butyl, tert-butyl or the like; more preferably, R is tert-butyl.
The invention also provides a preparation method of the piperazine modified tetraphenylethylene derivative, which is simple and easy to operate and mild in reaction conditions, and the preparation method comprises the following steps: under the protection of inert gas, dissolving 1- (4 '-bromophenyl) -1,2, 2-triphenylethylene, 4- (4' -carbonate-1-piperazinyl) phenylboronic acid pinacol ester and carbonate in an organic solvent A or a mixed solvent of the organic solvent A and water, adding a catalyst, and carrying out Suzuki coupling reaction; and after the reaction is finished, cooling the product mixture to room temperature, and carrying out post-treatment to obtain the piperazine modified tetraphenylethylene derivative shown as the formula I.
In the step (1), the reaction temperature of the Suzuki coupling reaction is 80-100 ℃, and the reaction time is 5-30 hours.
In the step (1), the catalyst is palladium tetratriphenylphosphine (Pd (Ph)3P)4) The dosage of the catalyst is 1-3% of the mass of 1- (4-bromophenyl) -1,2, 2-triphenylethylene.
In the step (1), the carbonate serves to provide an alkaline environment, the percentage concentration of the carbonate is determined to be 5-15% according to the amount of water in the mixed solvent, and one of sodium carbonate, potassium carbonate, cesium carbonate and lithium carbonate can be selected according to the conditions of raw materials and the solvent.
In the step (1), the organic solvent A is tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, dioxane or cyclohexanone.
In the step (1), the water content of the mixed solvent of the organic solvent A and water is 5-30% by volume ratio.
In the step (1), the molar ratio of the 1- (4 '-bromophenyl) -1,2, 2-triphenylethylene to the 4- (4' -carbonate-1-piperazinyl) phenylboronic acid pinacol ester is 1: 1.1-2.0, and the specific proportion is selected according to the used solvent and the reaction temperature.
In the step (1), the inert gas is high-purity nitrogen, common nitrogen or argon.
In the step (2), the post-treatment comprises the operations of concentration, extraction, rotary evaporation and purification; the concentration operation refers to removing the organic solvent A by rotary evaporation to leave a small amount of aqueous liquid; the extraction operation is that the concentrated residual liquid is extracted by a mixture of dichloromethane and saturated common salt water, wherein the volume ratio of the dichloromethane to the saturated common salt water is 0.5-3: 1, organic phases are combined, and a water phase is discarded; the rotary evaporation operation is to remove the organic solvent in the extract liquid by rotary evaporation; the purification operation refers to separating a product mixture through a silica gel chromatographic column, wherein the eluent is a mixed solvent prepared from dichloromethane and petroleum ether (60-90 ℃) according to a volume ratio of 1:1.
The chemical reaction equation for preparing the piperazine modified tetraphenylethylene derivative provided by the invention is as follows:
the piperazine modified tetraphenylethylene derivative provided by the invention can be used as a fluorescent probe molecule for detecting aromatic nitro explosives.
The piperazine modified tetraphenylethylene derivative is used as an identification unit of a probe molecule and is a piperazine group, a signal sensing unit is a Tetraphenylethylene (TPE) group with AIE performance, a connecting arm is a benzene ring and is linked through a covalent bond, the benzene ring of the connecting arm and the benzene ring of the TPE molecule of the signal sensing unit are in the same plane to form a large conjugated pi-bond system, and after the piperazine group identifies and is combined with an aromatic nitro explosive, the large conjugated pi-bond system of the probe molecule is destroyed, so that the fluorescence performance of the probe molecule is changed and is expressed as fluorescence quenching, and the effect of identifying the aromatic nitro explosive is achieved.
The invention provides a method for detecting aromatic nitro explosives by using piperazine modified tetraphenylethylene derivative shown as a formula I as a fluorescent probe molecule, which comprises the following steps:
(a) piperazine-modified tetraphenylethylene derivative shown as formula I is used as a fluorescent probe molecule, organic solvent B is used as a solvent, and the preparation concentration is 1-10 × 10-6A mol/L solution;
(b) adding water into the solution prepared in the step (a) to prepare a suspension of the piperazine modified tetraphenylethylene derivative;
(c) adding the aromatic nitro explosives into the suspension prepared in the step (b), detecting the change of the fluorescence intensity of the suspension system along with the content of the aromatic nitro explosives, and drawing a working curve of the fluorescence intensity of the suspension system along with the change of the concentration of the aromatic nitro explosives to obtain the lowest detection limit of the aromatic nitro explosives.
In the step (a), the organic solvent B is tetrahydrofuran, acetonitrile, N-dimethylformamide, dimethyl sulfoxide or dioxane.
In the step (B), the volume ratio of the added water to the organic solvent B is 80-90%.
The piperazine modified tetraphenylethylene derivative fluorescent probe molecule and the TNP molecule can be specifically complexed, a piperazine ring in the probe molecule is opened, a connecting arm benzene ring molecule is twisted, and a large conjugated system of the piperazine modified tetraphenylethylene derivative fluorescent probe molecule is greatly damaged.
The TNP detection method provided by the invention is simple, the reaction is rapid, and no additional catalyst is needed; the sensitivity for detecting TNP is high, the detection limit is low, and the lowest detection limit of TNP can reach the micromole (mu M) magnitude.
The raw materials for preparing the piperazine modified tetraphenylethylene derivative are commercial products, have low cost and easy obtainment, are suitable for industrial production, and are expected to be widely applied to the aspects of environmental pollution and public safety.
Compared with the prior art, the invention has the following beneficial effects:
1. the preparation method of the fluorescence detection substance provided by the invention is simple, the reaction conditions are mild, the raw materials are easy to obtain, the cost is low, and the method is suitable for industrial production.
2. The fluorescence detection method provided by the invention is simple and rapid in reaction, and can complete detection without an additional catalyst.
3. The fluorescence detection method provided by the invention has the advantages of high sensitivity, strong selection specificity and short response time; and the TNP can be specifically detected, and the minimum detection limit of the TNP can reach micromolar magnitude.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of 1- (4' -Boc-1-piperazinylphenyl) -1,2, 2-triphenylethylene prepared in example 1 of the present invention.
FIG. 2 is a nuclear magnetic resonance carbon spectrum of 1- (4' -Boc-1-piperazinylphenyl) -1,2, 2-triphenylethylene prepared in example 1 of the present invention.
FIG. 3 is an IR spectrum of 1- (4' -Boc-1-piperazinylphenyl) -1,2, 2-triphenylethylene prepared in example 1 of the present invention.
FIG. 4 is a graph showing the AIE performance of 1- (4' -Boc-1-piperazinylphenyl) -1,2, 2-triphenylethylene in example 1 of the performance test of the present invention;
FIG. 5 is a fluorescence spectrum of TNP detection using 1- (4' -Boc-1-piperazinylphenyl) -1,2, 2-triphenylethylene in application example 1 of the present invention.
FIG. 6 is a graph showing the relationship between the fluorescence intensity of the system and the concentration of TNP in the case of performing fluorescence detection of TNP using 1- (4' -Boc-1-piperazinylphenyl) -1,2, 2-triphenylethylene in application example 1 of the present invention.
FIG. 7 is a TNP concentration portion from 1. mu.M to 6. mu.M on a TNP concentration curve showing the change of the fluorescence intensity of the system with respect to the TNP concentration when TNP is subjected to fluorescence detection using 1- (4' -Boc-1-piperazinylphenyl) -1,2, 2-triphenylethylene in application example 1 of the present invention. The fluorescence intensity of the interval system approaches a linear relation along with the change of the TNP concentration, and the detection lower limit is favorably determined.
Detailed Description
For further understanding of the present invention, the piperazine modified tetraphenylethylene derivative and its use provided by the present invention are specifically described below with reference to the following examples, but the present invention is not limited to these examples. The non-essential modification and adjustment made by the person skilled in the art guided by the above disclosure of the invention still belong to the protection scope of the invention.
EXAMPLE 11 Synthesis of- (4' -Boc-1-piperazinylphenyl) -1,2, 2-triphenylethylene
Under the protection of high-purity nitrogen, 411mg of 1- (4 ' -bromophenyl) -1,2, 2-triphenylethylene, 485mg of 4- (4 ' -Boc-1-piperazinyl) phenylboronic acid pinacol ester and 160mg of sodium carbonate (molar ratio of 1: 1.2: 1.5) are mixed and dissolved in a mixed solvent prepared from 80mL of tetrahydrofuran and 20mL of water (volume ratio of 4:1), 6.2mg of tetratriphenylphosphine palladium catalyst is added after complete dissolution, the amount of the tetratriphenylphosphine palladium catalyst is 1.5 wt% of 1- (4 ' -bromophenyl) -1,2, 2-triphenylethylene, and the mixture is refluxed in an oil bath at 90 ℃. After 12 hours of reaction, the oil bath was removed and the system was allowed to cool naturally to room temperature. A portion of the organic solvent was removed by rotary evaporator and the mixture was concentrated to 1/3. And then extracting the system with dichloromethane and saturated saline water 60mL in a volume ratio of 1: 2 for three times, collecting an organic phase, removing water with anhydrous sodium sulfate, determining the dosage of a drying agent according to the volume of the extraction liquid, adding 2g of anhydrous sodium sulfate into each 100mL of the extraction liquid, and standing for 8-12 hours. Filtering at normal pressure to remove the water-absorbing desiccant anhydrous sodium sulfate, and removing the organic solvents dichloromethane and tetrahydrofuran on a rotary evaporator; and (3) separating the obtained residual solid by using a mixed solvent of petroleum ether (60-90 ℃) and dichloromethane in a volume ratio of 1:1 as an eluent through column chromatography to finally obtain the compound 1- (4' -Boc-1-piperazinylphenyl) -1,2, 2-triphenylethylene with the yield of 76.6%. The chemical structure is identified by nuclear magnetic hydrogen spectrum, nuclear magnetic resonance carbon spectrum and infrared absorption spectrum; the hydrogen nuclear magnetic resonance spectrum is shown in FIG. 1, the carbon nuclear magnetic resonance spectrum is shown in FIG. 2, and the infrared absorption spectrum is shown in FIG. 3.
EXAMPLE 21 Synthesis of (4' -Boc-1-piperazinylphenyl) -1,2, 2-triphenylethylene
Under the protection of common nitrogen, 411mg of 1- (4 ' -bromophenyl) -1,2, 2-triphenylethylene, 606mg of 4- (4 ' -Boc-1-piperazinyl) phenylboronic acid pinacol ester and 202mg of potassium carbonate (molar ratio is 1: 1.5) are mixed and dissolved in a mixed solvent prepared from 100mL of acetonitrile and 20mL of water (volume ratio is 5:1), 8.2mg of tetratriphenylphosphine palladium catalyst is added after complete dissolution, the amount of the tetratriphenylphosphine palladium catalyst is 2.0 wt% of 1- (4 ' -bromophenyl) -1,2, 2-triphenylethylene, and the mixture is heated and refluxed in an oil bath at 100 ℃. After 10 hours of reaction, the oil bath was removed and the system was allowed to cool naturally to room temperature. A portion of the organic solvent was removed by rotary evaporator and the mixture was concentrated to 1/3. And then extracting the system with dichloromethane and saturated saline solution 60mL in a volume ratio of 1: 2 for three times, collecting an organic phase, adding 5g of anhydrous magnesium sulfate, and standing for 8-12 hours. Filtering at normal pressure, removing anhydrous magnesium sulfate as absorbent drying agent, and removing acetonitrile solvent of dichloromethane on a rotary evaporator; and (3) separating the obtained residual solid by using a mixed solvent of petroleum ether (60-90 ℃) and dichloromethane in a volume ratio of 1:1 as an eluent through column chromatography to finally obtain the compound 1- (4' -Boc-1-piperazinylphenyl) -1,2, 2-triphenylethylene with the yield of 58.1%. The chemical structure of the compound was identified according to synthetic example 1.
EXAMPLE 31 Synthesis of (4' -Boc-1-piperazinylphenyl) -1,2, 2-triphenylethylene
Under the protection of argon, 410mg of 1- (4 ' -bromophenyl) -1,2, 2-triphenylethylene, 485mg of 4- (4 ' -Boc-1-piperazinyl) phenylboronic acid pinacol ester and 160mg of sodium carbonate (molar ratio of 1: 1.2: 1.5) are mixed and dissolved in a mixed solvent prepared from 80mL of tetrahydrofuran and 20mL of water (volume ratio of 4:1), 6.2mg of tetratriphenylphosphine palladium catalyst is added after complete dissolution, the amount of the tetratriphenylphosphine palladium catalyst is 1.5 wt% of 1- (4 ' -bromophenyl) -1,2, 2-triphenylethylene, and the mixture is refluxed in an oil bath at 90 ℃. After 18 hours of reaction, the oil bath was removed and the system was allowed to cool to room temperature. A portion of the organic solvent was removed by rotary evaporator and the mixture was concentrated to 1/3. And then extracting the system with dichloromethane and saturated saline solution 60mL in a volume ratio of 1: 2 for three times, collecting an organic phase, removing water with 4g of anhydrous magnesium sulfate, and standing the system for 8-12 hours. Filtering at normal pressure to remove the water-absorbing drying agent, and removing the organic solvent on a rotary evaporator; and (3) separating the obtained residual solid by using a mixed solvent of petroleum ether (60-90 ℃) and dichloromethane in a volume ratio of 1:1 as an eluent through column chromatography to finally obtain the compound 1- (4' -Boc-1-piperazinylphenyl) -1,2, 2-triphenylethylene with the yield of 77.5%. The chemical structure of the compound was identified according to synthetic example 1.
EXAMPLE 41 Synthesis of (4' -Boc-1-piperazinylphenyl) -1,2, 2-triphenylethylene
Under the protection of high-purity nitrogen, 1234mg of 1- (4 ' -bromophenyl) -1,2, 2-triphenylethylene, 1578mg of 4- (4 ' -Boc-1-piperazinyl) phenylboronic acid pinacol ester and 636mg of sodium carbonate (molar ratio of 1: 1.3: 2.0) are mixed and dissolved in a mixed solvent prepared from 120mL of dioxane and 30mL of water (volume ratio of 4:1), 22.2mg of tetratriphenylphosphine palladium catalyst is added after complete dissolution, the amount of the tetratriphenylphosphine palladium catalyst is 1.8 wt% of 1- (4 ' -bromophenyl) -1,2, 2-triphenylethylene, and the mixture is refluxed in an oil bath at 90 ℃. After 12 hours of reaction, the oil bath was removed and the system was allowed to cool naturally to room temperature. A portion of the organic solvent was removed by rotary evaporator and the mixture was concentrated to 1/3. Then, the system is extracted by dichloromethane and saturated saline solution 60mL with the volume ratio of 1: 2 for four times, the organic phase is collected and is dewatered by 8g of anhydrous magnesium sulfate, and the system is kept still for 12 hours. Filtering at normal pressure to remove the water-absorbing drying agent, and removing the solvent on a rotary evaporator; and (3) separating the obtained residual solid by using a mixed solvent of petroleum ether (60-90 ℃) and dichloromethane in a volume ratio of 1:1 as an eluent through column chromatography to finally obtain the compound 1- (4' -Boc-1-piperazinylphenyl) -1,2, 2-triphenylethylene with the yield of 81.1%. The chemical structure of the compound was identified according to synthetic example 1.
EXAMPLE 51 Synthesis of (4' -Boc-1-piperazinylphenyl) -1,2, 2-triphenylethylene
Under the protection of high-purity nitrogen, 410mg of 1- (4 ' -bromophenyl) -1,2, 2-triphenylethylene, 485mg of 4- (4 ' -Boc-1-piperazinyl) phenylboronic acid pinacol ester and 112mg of lithium carbonate (molar ratio of 1: 1.2: 1.5) are mixed and dissolved in a mixed solvent prepared from 80mL of tetrahydrofuran and 20mL of water (volume ratio of 4:1), 6.2mg of tetratriphenylphosphine palladium catalyst is added after complete dissolution, the amount of the tetratriphenylphosphine palladium catalyst is 1.5 wt% of 1- (4 ' -bromophenyl) -1,2, 2-triphenylethylene, and the mixture is refluxed in an oil bath at 90 ℃. After 18 hours of reaction, the oil bath was removed and the system was allowed to cool to room temperature. A portion of the organic solvent was removed by rotary evaporator and the mixture was concentrated to 1/3. And then extracting the system with dichloromethane and saturated saline water 60mL at a volume ratio of 1: 2 for three times, collecting the organic phase, dehydrating the organic phase with anhydrous sodium sulfate, determining the dosage of a drying agent according to the volume of the extract, adding 2g of anhydrous magnesium sulfate into each 100mL of extract, and standing for 8 hours. Filtering at normal pressure to remove the water-absorbing drying agent, and removing the solvent on a rotary evaporator; and (3) separating the obtained residual solid by using a mixed solvent of petroleum ether (60-90 ℃) and dichloromethane in a volume ratio of 1:1 as an eluent through column chromatography to finally obtain the compound 1- (4' -Boc-1-piperazinylphenyl) -1,2, 2-triphenylethylene with the yield of 69.5%. The chemical structure of the compound was identified according to synthetic example 1.
EXAMPLE 61 Synthesis of (4' -Boc-1-piperazinylphenyl) -1,2, 2-triphenylethylene
Under the protection of high-purity nitrogen, 615mg of 1- (4 ' -bromophenyl) -1,2, 2-triphenylethylene, 728mg of 4- (4 ' -Boc-1-piperazinyl) phenylboronic acid pinacol ester and 202mg of potassium carbonate (molar ratio of 1: 1.5) are mixed and dissolved in a mixed solvent prepared from 100mL of N, N-dimethylformamide and 20mL of water (volume ratio of 5:1), 8.2mg of tetratriphenylphosphine palladium catalyst is added after complete dissolution, the amount of the tetratriphenylphosphine palladium catalyst is 2 wt% of 1- (4 ' -bromophenyl) -1,2, 2-triphenylethylene, and the oil bath is removed after the reaction is carried out for 8 hours under the heating of the oil bath at 100 ℃, so that the system is naturally cooled to room temperature. A portion of the organic solvent was removed under reduced pressure using a rotary evaporator and the mixture was concentrated to 1/3. And then extracting the concentrated solution for three times by using dichloromethane and saturated saline solution 50mL with the volume ratio of 1: 2, collecting and combining organic phases, performing water removal treatment on the organic phases by using 4g of anhydrous magnesium sulfate, and standing for 8-12 hours. Filtering at normal pressure to remove the water-absorbing drying agent, and removing the solvent on a rotary evaporator; and (3) separating the obtained residual solid by using a mixed solvent of petroleum ether (60-90 ℃) and dichloromethane in a volume ratio of 1:1 as an eluent through column chromatography to finally obtain the compound 1- (4' -Boc-1-piperazinylphenyl) -1,2, 2-triphenylethylene with the yield of 72.3%. The chemical structure of the compound was identified according to synthetic example 1.
AIE Performance test example 1
The tetraphenylethylene derivative has AIE performance, and the detection steps are as follows:
1- (4' -Boc-1-piperazinylphenyl) -1,2, 2-triphenylethylene prepared in example 1 was dissolved in tetrahydrofuran to prepare a solution having a concentration of 1 × 10-4M mother liquor, taking 1mL of mother liquor, transferring the mother liquor to a 10mL volumetric flask, adding tetrahydrofuran with calculated amount, dropwise adding deionized water under rapid stirring to constant volume, and finally preparing the mother liquor with the concentration of 1 × 10-5M and the water content of the mixed solution is 0-90% respectively, and the water content is volume percentage.
And (3) rapidly transferring the solutions to a sample rack of a fluorescence spectrometer for fluorescence spectrum testing, wherein the excitation wavelength is 350nm, and the wavelength of the absorption peak with the lowest energy according to the ultraviolet-visible absorption spectrum of the solutions is selected. The test instrument is a Perkinelmer LS 55 type fluorescence spectrometer, the measured fluorescence spectrogram is summarized in figure 4, and the spectrum in the figure shows that when the water content in the tetrahydrofuran solution of the compound reaches 30 percent, the fluorescence of the compound I begins to appear; the fluorescence intensity gradually increased with the increase of the water content, indicating that the compound has AIE performance.
AIE Performance test example 2
The tetraphenylethylene derivative has AIE performance, and the test steps are as follows:
1- (4' -Boc-1-piperazinylphenyl) -1,2, 2-triphenylethylene prepared in example 1 was dissolved in acetonitrile solvent to prepare a solution having a concentration of 1 × 10-4M mother liquor 1mL mother liquor is transferred to a 10mL volumetric flask, acetonitrile with calculated amount is added, deionized water is dripped under rapid stirring for constant volume, and finally the mother liquor with the concentration of 1 × 10 is prepared-5M and the water content of the mixed solution is 0-90% respectively, and the water content is volume percentage.
And (3) rapidly transferring the solutions to a sample rack of a fluorescence spectrometer for fluorescence spectrum testing, wherein the excitation wavelength is 350nm, and the wavelength of the absorption peak with the lowest energy according to the ultraviolet-visible absorption spectrum of the solutions is selected. The test instrument was a Perkinelmer LS 55 type fluorescence spectrometer. When the water content of the acetonitrile solution of the compound reaches 50%, the fluorescence of the compound I begins to appear; the fluorescence intensity gradually increased with the continued increase in water content, indicating that the compound has AIE properties.
AIE Performance test example 3
The tetraphenylethylene derivative has AIE performance, and the test steps are as follows:
1- (4' -Boc-1-piperazinylphenyl) -1,2, 2-triphenylethylene prepared in example 1 was dissolved in dioxane to prepare a solution having a concentration of 1 × 10-4M mother liquor 1mL mother liquor is transferred to a 10mL volumetric flask, calculated amount of dioxane is added, deionized water is added dropwise under rapid stirring to constant volume, and finally the solution is prepared to have the concentration of 1 × 10-5M and the water content of the mixed solution is 0-90% respectively, and the water content is volume percentage.
And (3) rapidly transferring the solutions to a sample rack of a fluorescence spectrometer for fluorescence spectrum testing, wherein the excitation wavelength is 350nm, and the wavelength of the absorption peak with the lowest energy according to the ultraviolet-visible absorption spectrum of the solutions is selected. The test instrument was a Perkinelmer LS 55 type fluorescence spectrometer. When the water content in the tetrahydrofuran solution of the compound reaches 50%, the fluorescence of the compound I begins to appear; the fluorescence intensity gradually increased with the increase of the water content, indicating that the compound has AIE performance.
AIE Performance test example 4
The tetraphenylethylene derivative has AIE performance, and the test steps are as follows:
1- (4' -Boc-1-piperazinylphenyl) -1,2, 2-triphenylethylene prepared in example 1 was dissolved in dimethyl sulfoxide to prepare a solution having a concentration of 1 × 10-4Transferring 1mL of mother liquor into a 10mL volumetric flask, adding dimethyl sulfoxide with calculated amount, dropwise adding deionized water under rapid stirring to constant volume, and finally preparing the mother liquor with the concentration of 1 × 10-5M and the water content of the mixed solution is 0-90% respectively, and the water content is volume percentage.
And (3) rapidly transferring the solutions to a sample rack of a fluorescence spectrometer for fluorescence spectrum testing, wherein the excitation wavelength is 350nm, and the wavelength of the absorption peak with the lowest energy according to the ultraviolet-visible absorption spectrum of the solutions is selected. The test instrument was a Perkinelmer LS 55 type fluorescence spectrometer. When the water content in the compound in dimethyl sulfoxide solution reaches 60%, the fluorescence of the compound I begins to appear; the fluorescence intensity gradually increased with the increase of the water content, indicating that the compound has AIE performance.
AIE Performance test example 5
The detection steps of the AIE performance of the tetraphenylethylene derivative provided by the invention are as follows:
1- (4' -Boc-1-piperazinylphenyl) -1,2, 2-triphenylethylene prepared in example 1 was dissolved in N, N-dimethylformamide and prepared to have a concentration of 1 × 10-4Transferring 1mL of mother liquor into a 10mL volumetric flask, adding calculated amount of N, N-dimethylformamide, dropwise adding deionized water under rapid stirring to constant volume, and finally preparing the mother liquor with the concentration of 1 × 10-5M and the water content of the mixed solution is 0-90% respectively, and the water content is volume percentage.
And (3) rapidly transferring the solutions to a sample rack of a fluorescence spectrometer for fluorescence spectrum testing, wherein the excitation wavelength is 350nm, and the wavelength of the absorption peak with the lowest energy according to the ultraviolet-visible absorption spectrum of the solutions is selected. The test instrument was a Perkinelmer LS 55 type fluorescence spectrometer. When the water content of the N, N-dimethylformamide solution of the compound reaches 60%, the fluorescence of the compound I begins to appear; the fluorescence intensity gradually increased with the increase of the water content, indicating that the compound has AIE performance.
TNP detection application example 1
The AIE molecule can be used for detecting TNP, and the detection steps are as follows:
1- (4' -Boc-1-piperazinylphenyl) -1,2, 2-triphenylethylene was added at a concentration of 1 × 10-5M and the water content is respectively 90 percent, wherein the organic solvent is one of tetrahydrofuran, acetonitrile, dioxane, dimethyl sulfoxide and N, N-dimethylformamide, and the water content is volume percentage. Taking a tetrahydrofuran/water mixed solvent as an example, the method comprisesTNP was added to the fluorescence detection medium at a concentration of from 1 x 10-6M gradually increased to 5 x 10-5And M. The fluorescence intensity of the detection system gradually decreases with increasing concentration of TNP. Adding 1 x 10-6The TNP of M caused a significant decrease in the fluorescence intensity of the detection system, and the data shown in FIG. 5 indicated a 10% decrease in fluorescence intensity. The fluorescence intensity I was plotted against the TNP concentration to obtain the curves of the fluorescence intensity of the system as a function of the TNP concentration shown in FIGS. 6 and 7, and the TNP detection limit was determined to be 1 x 10 on the curves-6M。
The detection method using acetonitrile, dioxane, dimethyl sulfoxide, and N, N-dimethylformamide as an organic solvent was the same as in TNP detection application example 1 described above.
Claims (9)
1. A piperazine modified tetraphenylethylene derivative has a structural formula shown in formula I:
wherein R is tert-butyl.
2. A method for producing the piperazine-modified tetraphenylethylene derivative of claim 1, comprising:
under the protection of inert gas, dissolving 1- (4 '-bromophenyl) -1,2, 2-triphenylethylene, 4- (4' -Boc-1-piperazinyl) phenylboronic acid pinacol ester and carbonate in an organic solvent A or a mixed solvent of the organic solvent A and water, adding a catalyst, and carrying out Suzuki coupling reaction; and after the reaction is finished, cooling the product mixture to room temperature, and carrying out post-treatment to obtain the piperazine modified tetraphenylethylene derivative shown as the formula I.
3. The method for preparing the piperazine-modified tetraphenylethylene derivative of claim 2, wherein the Suzuki coupling reaction conditions are as follows: the catalyst is palladium tetratriphenylphosphine, the reaction temperature is 80-100 ℃, and the reaction time is 5-30 hours.
4. The method for preparing the piperazine-modified tetraphenylethylene derivative of claim 2, wherein the organic solvent a is tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, dioxane, or cyclohexanone; the mixed solvent of the organic solvent A and water contains 5-30% of water by volume ratio.
5. The preparation method of the piperazine modified tetraphenylethylene derivative according to claim 2, wherein the molar ratio of 1- (4 '-bromophenyl) -1,2, 2-triphenylethylene to 4- (4' -Boc-1-piperazinyl) phenylboronic acid pinacol ester is 1: 1.1-2.0; the usage amount of the tetratriphenylphosphine palladium is 1-3 wt% of 1- (4' -bromophenyl) -1,2, 2-triphenylethylene.
6. The use of the piperazine modified tetraphenylethylene derivative of claim 1 as a fluorescent probe molecule in the field of detection of aromatic nitro explosives.
7. The use of claim 6, wherein the aromatic nitro-explosive is 2,4, 6-trinitrophenol.
8. The use according to claim 6 or 7, in particular comprising:
(a) piperazine modified tetraphenylethylene derivative shown as formula I is used as fluorescent substance, organic solvent B is used as solvent, and the preparation concentration is 1-10 × 10-6A mol/L solution;
(b) adding water into the solution prepared in the step (a) to prepare a suspension of the piperazine modified tetraphenylethylene derivative;
(c) adding the aromatic nitro explosives into the suspension prepared in the step (b), detecting the change of the fluorescence intensity of the suspension system along with the content of the aromatic nitro explosives, and drawing a working curve of the fluorescence intensity of the suspension system along with the change of the concentration of the aromatic nitro explosives to obtain the lowest detection limit of the aromatic nitro explosives.
9. The use according to claim 8, wherein in step (a), the organic solvent B is tetrahydrofuran, acetonitrile, N-dimethylformamide, dimethyl sulfoxide or dioxane; in the step (B), the volume ratio of the added water to the organic solvent B is 80-90%.
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