CN113121469B

CN113121469B - Red light material and preparation method and application thereof

Info

Publication number: CN113121469B
Application number: CN202110293517.4A
Authority: CN
Inventors: 刘聪; 杨京莲; 罗运源; 戴慧; 利颖蓉; 石光; 顾凤龙
Original assignee: South China Normal University
Current assignee: South China Normal University
Priority date: 2021-03-19
Filing date: 2021-03-19
Publication date: 2023-01-10
Anticipated expiration: 2041-03-19
Also published as: CN113121469A

Abstract

The invention belongs toThe technical field of luminescent materials, and discloses a red light material, and a preparation method and application thereof. The red light material has the structural formula as follows:

wherein D represents an electron donating group and π represents a π conjugated group. The red light material takes benzothiadiazole as a luminescent nucleus, one side of the diazosulfide is connected with an electron donating group, and the other side of the diazosulfide is connected with a secondary amino group and a pi conjugated group to form a D-A type molecule. The red light material is used as a fluorescent probe, has high sensitivity, good selectivity and low detection limit, can simultaneously detect fluorine ions and 2,4,6-trinitrophenol, and has the detection limit for detecting 2,4,6-Trinitrophenol (TNP) as low as 5.30 multiplied by 10 ^‑9 mol/L. The preparation method of the red light material is simple.

Description

Red light material and preparation method and application thereof

Technical Field

The invention belongs to the technical field of luminescent materials, and particularly relates to a red light material, and a preparation method and application thereof.

Background

2,4,6-Trinitrophenol (TNP) is one of the explosive substances with great power in nitroaromatic explosives, causes huge pollution to soil and water environment, and is a potential soil and water pollutant. The traditional TNP detection method comprises a chromatographic method, an ion transfer method, a spectroscopic method and the like. These methods often require expensive equipment and are complicated and time consuming to operate. The TNP in the water body environment is detected, the content of the TNP in the water body is favorably controlled, the environmental pollution is reduced, and the human health is ensured.

The fluorine ions are the anions with the strongest electronegativity and the smallest ionic radius, and have important functions in the fields of chemistry, biology, medicine and the like. The fluorine ions are one of the trace elements necessary for human body, and a proper amount of fluorine can play the roles of strengthening bones and teeth, preventing the dissolution of the tooth surface and promoting the re-solidification of the dissolved surface, and can effectively prevent and treat dental caries, osteoporosis and the like. However, the metabolism of fluorine ions in human body is very slow, the excessive fluorine will cause permanent and irreversible damage to human body, and the long-term intake of excessive fluorine will cause many diseases and affect growth and development. Therefore, the concentration of fluorine ions in the water body is also concerned.

The detection method of the fluorescent probe has the advantages of high selectivity, high sensitivity, convenience, rapidness, low cost and the like, but the existing detection method has fewer fluorescent probes capable of detecting 2,4,6-trinitrophenol and fluorine ions, and no fluorescent probe capable of simultaneously detecting 2,4,6-trinitrophenol and fluorine ions in a water body.

Therefore, it is desirable to provide a fluorescent probe capable of detecting 2,4,6-trinitrophenol and fluoride ions simultaneously.

Disclosure of Invention

The present invention has been made to solve at least one of the above-mentioned problems occurring in the prior art. Therefore, the invention provides a red light material, and the red light material is used for preparing a fluorescent probe and can be used for simultaneously detecting 2,4,6-trinitrophenol and fluorine ions.

A red light material has a structural formula as follows:

wherein D represents an electron donating group, and π represents a π conjugated group.

Preferably, the electron donating group is an aniline or carbazole containing group.

Further preferably, the electron-donating group is one selected from the group consisting of groups represented by formula (1), formula (2) and formula (3),

preferably, the pi conjugated group is an aromatic group; further preferably, the pi conjugated group is at least one selected from the group consisting of groups represented by formula (4), formula (5), formula (6) and formula (7),

wherein R is ₁ 、R ₂ 、R ₃ And R ₄ Each independently represents-H, -NO ₂ -CN, -CHO or-CF ₃ One kind of (1).

Preferably, the red light material is a compound with a structural formula shown as a formula (8) or a formula (9),

the invention also provides a preparation method of the red light material, which comprises the following steps:

(1) Preparing an intermediate containing an electron donating group and benzothiadiazole;

(2) Adding an aromatic compound containing secondary amine groups into the intermediate prepared in the step (1) to prepare the red light material.

Specifically, the preparation method of the red light material comprises the following steps:

(1) A compound containing a benzothiadiazole structure, a compound containing an aniline or carbazole structure, and Cs ₂ CO ₃ And Ruphos (2-dicyclohexylphosphine-2 ',6' -diisopropoxybiphenyl) and a catalyst are dissolved in a solvent, mixed, reacted, cooled and extracted to prepare the intermediate.

(2) Adding aromatic compounds containing secondary amino and Cs into the intermediate prepared in the step (1) ₂ CO ₃ And Ruphos (2-dicyclohexylphosphine-2 ',6' -diisopropoxybiphenyl) and a catalyst are dissolved in a solvent, and the red light material is prepared by mixing, reacting, cooling and extracting.

Preferably, the reaction temperature in the step (1) is 110-120 ℃, and the reaction time in the step (1) is 12-48h.

Preferably, the reaction temperature in the step (2) is 110-120 ℃, and the reaction time in the step (1) is 12-48h.

Preferably, the aromatic compound containing a secondary amine group in step (2) is p-aminobenzonitrile.

The invention also provides application of the red light material in preparation of a fluorescent probe.

The application of the red light material in detecting fluoride ions.

The red light material is applied to detection of 2,4,6-trinitrophenol.

According to the red light material provided by the invention, benzothiadiazole is used as a luminescent nucleus, is an extremely strong electron-withdrawing group and has a large Stokes shift (Stokes shift), one side of the benzothiadiazole is connected with the electron-withdrawing group to form a D-A structure, and a propeller structure is formed, so that intermolecular pi-pi accumulation is inhibited, and the luminous efficiency is enhanced; the other side is connected with a secondary amine group, an intramolecular hydrogen bond is easily formed, and excited state proton transfer (ESIPT) occurs. The red light material has Aggregation Induced Emission (AIE) and Intramolecular Charge Transfer (ICT) properties, contains a strong electron-withdrawing group, is favorable for deprotonation of molecules, and is favorable for detecting fluoride ions and 2,4,6-trinitrophenol.

Compared with the prior art, the invention has the following beneficial effects:

(1) The red light material provided by the invention takes benzothiadiazole as a luminescent nucleus, one side of the benzothiadiazole is connected with an electron donating group, and the other side of the benzothiadiazole is connected with a secondary amino group and a pi conjugated group to form a D-A type (containing a donor and an acceptor) molecule. The red light material can be used as a fluorescent probe, and has high sensitivity, good selectivity and low detection limit. Can simultaneously detect fluorinion and 2,4,6-trinitrophenol, and the detection limit for detecting 2,4,6-Trinitrophenol (TNP) is as low as 5.30 multiplied by 10 ^-9 mol/L。

(2) The preparation method of the red light material provided by the invention is simple.

Drawings

FIG. 1 is a mass spectrum of a red-light material prepared in example 1;

FIG. 2 is a mass spectrum of a red-light material prepared in example 2;

FIG. 3 is a graph showing fluorescence spectra of the red-emitting material prepared in example 1 in different solvents;

FIG. 4 is a graph of fluorescence spectra of red-emitting materials prepared in example 2 in different solvents;

FIG. 5 shows DMSO/H of the red light material prepared in example 1 at different volume fractions of water ₂ Fluorescence spectrum in O solution;

FIG. 6 is a graph showing the fluorescence intensity of the red-emitting material prepared in example 1 in different volume fractions of water;

FIG. 7 shows DMSO/H of red light materials prepared in example 2 at different water volume fractions ₂ Fluorescence spectrum in O solution;

FIG. 8 is a graph showing the fluorescence intensity of the red-emitting material prepared in example 2 in different volume fractions of water;

FIG. 9 is a graph of the fluorescence spectra of the red-emitting materials prepared in example 1 with different anions added;

FIG. 10 is a graph of the UV-VIS absorption spectra of the red-emitting materials prepared in example 2 with different anions added;

FIG. 11 is a graph showing the fluorescence spectra of the red-emitting material prepared in example 2 with different anions added;

FIG. 12 is a fluorescence spectrum of the red-emitting material prepared in example 1 for detecting different nitro explosives;

FIG. 13 is a graph of the fluorescent titration of TNP for red-emitting materials prepared in example 1;

FIG. 14 shows the results of measurement I of the red-emitting material obtained in example 1 ₀ The trend of the/I-1 value with the TNP concentration;

FIG. 15 shows the result I of the detection of the red-light emitting material obtained in example 1 ₀ -a fitted curve of I versus TNP concentration;

FIG. 16 is a fluorescence spectrum of the red-emitting material prepared in example 2 for detecting different nitro explosives;

FIG. 17 is a graph of the fluorescent titration of TNP for red-emitting materials prepared in example 2;

FIG. 18 shows the results of measurement I of the red-emitting material obtained in example 2 ₀ The trend of the/I-1 value with the TNP concentration;

FIG. 19 shows an example of use2 detection of the prepared Red light Material I ₀ -I fitted curve to TNP concentration.

Detailed Description

In order to make the technical solutions of the present invention more clearly apparent to those skilled in the art, the following examples are given for illustration. It should be noted that the following examples are not intended to limit the scope of the claimed invention.

The starting materials, reagents or apparatuses used in the following examples are conventionally commercially available or can be obtained by conventionally known methods, unless otherwise specified.

Example 1

A red light material has the following structural formula (mass spectrum shown in figure 1):

the preparation method of the red light material comprises the following steps:

(1) Preparation of intermediate DP-BTD-Br

A250 mL three-necked flask was charged with 4,7-dibromo-2,1,3-benzothiadiazole 1.76g (6 mmol), diphenylamine 0.85g (5 mmol), cs ₂ CO ₃ 4g (8.7 mmol) and 0.10g (0.3 mmol) of Ruphos were dissolved in 25mL of toluene, magnetically stirred and bubbled with Ar gas for 40 minutes, then the reaction temperature was adjusted to 110 ℃ and 3mg of catalyst Pd was added ₂ (dba) ₃ And reacting for 24 hours under an Ar atmosphere. The reaction was cooled to room temperature, then poured into saturated brine, extracted three times with dichloromethane, dried with excess anhydrous magnesium chloride, vacuum filtered, rotary evaporated to give an orange solid, the crude product was further purified by silica gel column chromatography (eluent DCM/PE = 1) to give an orange solid, yield: 62.1 percent. The results of nuclear magnetic characterization were: ¹ H NMR(600MHz,CDCl ₃ )δ7.68(d,J＝8.0Hz,1H),7.29–7.27(m,3H),7.26(s,1H),7.09(t,J＝7.4Hz,2H),7.05(dd,J＝8.5,1.0Hz,4H),7.03(d,J＝8.0Hz,1H).ESI-MS m/z:[M] ⁺ calcd.for 382.2770；found,382.0007。

(2) Preparation of Red light Material DP-BTD-CN

Taking 0.24g (0.63 mmol) of DP-BTD-Br prepared in the step (1), and 0.063g (0.53 mmol) of para-aminobenzonitrile, cs ₂ CO ₃ 0.39g (1.2 mmol) and 0.0140g (0.03 mmol) of Ruphos were dissolved in 25mL of toluene, magnetically stirred and bubbled with Ar gas for 40 minutes, then the reaction temperature was adjusted to 110 ℃ and 3mg of catalyst Pd was added ₂ (dba) ₃ And reacting for 24 hours under an Ar atmosphere. Cooling the reaction system to room temperature, then pouring into saturated brine, extracting with dichloromethane three times, adding excess anhydrous magnesium chloride, drying overnight, vacuum filtering, rotary evaporating to obtain brick red solid, further purifying the crude product by silica gel column chromatography (eluent is DCM/PE = 3:1) to obtain brick red solid, yield: 86.4 percent. The results of nuclear magnetic characterization were: ¹ H NMR(600MHz,DMSO)δ9.43(s,1H),7.66(d,J＝8.7Hz,2H),7.45(d,J＝8.0Hz,1H),7.35(d,J＝8.8Hz,2H),7.29(d,J＝8.0Hz,1H),7.24(t,J＝7.9Hz,4H),6.99(d,J＝8.1Hz,4H),6.97(s,2H). ¹³ C NMR(151MHz,DMSO)δ152.14,150.44,147.25,133.47,132.39,130.49,129.24,127.69,122.37,122.34,119.73,116.69,114.41,100.76.ESI-MS m/z:[M] ⁺ calcd.for 419.5051；found,418.1133。

example 2

The red light material has the following structural formula (mass spectrum shown in figure 2):

the preparation method of the red light material comprises the following steps:

(1) Preparation of intermediate DP-BTD-Br

Into a 250mL three-necked flask was charged 4,7-dibromo-2,1,3-benzothiadiazole 1.76g (6 mmol), diphenylamine 0.85g (5 mmol), cs ₂ CO ₃ 4g (8.7 mmol) and 0.10g (0.3 mmol) of Ruphos were dissolved in 25mL of toluene, magnetically stirred and bubbled with Ar gas for 40 minutes, then the reaction temperature was adjusted to 110 ℃ and 3mg of catalyst Pd was added ₂ (dba) ₃ And reacting for 24 hours under an Ar atmosphere. Cooling the reaction system to room temperature, pouring into saturated salt water, and separating with dichloromethaneThe extraction was repeated, excess anhydrous magnesium chloride was added, dried, vacuum filtered, rotary evaporated to give an orange solid, and the crude product was further purified by silica gel column chromatography (eluent DCM/PE = 1): 62.1 percent. The results of nuclear magnetic characterization were: ¹ H NMR(600MHz,CDCl ₃ )δ7.68(d,J＝8.0Hz,1H),7.29–7.27(m,3H),7.26(s,1H),7.09(t,J＝7.4Hz,2H),7.05(dd,J＝8.5,1.0Hz,4H),7.03(d,J＝8.0Hz,1H).ESI-MS m/z:[M] ⁺ calcd.for 382.2770；found,382.0007。

(2) Preparation of red light material DP-BTD-TPE

Taking 0.27g (0.7 mmol) of DP-BTD-Br prepared in the step (1) and 0.12g (0.36 mmol) of 1- (4-aminobenzene) -1,2,2-triphenylethylene and Cs ₂ CO ₃ 0.26g (0.8 mmol) and 0.0140g (0.03 mmol) of Ruphos were dissolved in 25mL of toluene, magnetically stirred and bubbled with Ar gas for 40 minutes, then the reaction temperature was adjusted to 110 ℃ and 3mg of catalyst Pd was added ₂ (dba) ₃ And reacting for 24 hours under an Ar atmosphere. The reaction was cooled to room temperature, then poured into saturated brine, extracted three times with dichloromethane, dried overnight with excess anhydrous magnesium chloride, vacuum filtered, rotary evaporated to give a red solid, and the crude product was further purified by silica gel column chromatography (eluent DCM/PE = 1:1) to give a red solid, yield: 82.6 percent. The results of nuclear magnetic characterization were: ¹ H NMR(600MHz,DMSO)δ8.81(s,1H),7.28(d,J＝8.0Hz,1H),7.23–7.20(m,3H),7.20–7.19(m,1H),7.18–7.14(m,5H),7.10(dtd,J＝13.1,9.4,4.5Hz,7H),7.04–7.01(m,4H),6.97–6.92(m,8H),6.92–6.88(m,2H). ¹³ C NMR(151MHz,DMSO)δ152.58,149.49,147.32,143.56,143.47,143.38,140.37,140.03,139.82,136.42,133.84,131.58,130.76,130.04(s,2H),129.19,128.82,127.92,127.83,127.80,126.53,126.47,126.39,121.88,121.64,118.52,107.42.ESI-MS m/z:[M] ⁺ calcd.for 648.2348；found,647.2277。

product effectiveness testing

1. The light emitting properties of the red light emitting materials prepared in examples 1 and 2 were measured

Both the DP-BTD-CN molecule (prepared from example 1) and the DP-BTD-TPE molecule (prepared from example 2) contain the strongly electron withdrawing group Benzothiadiazole (BTD) and the electron donating group Diphenylamine (DP), belonging to the D-A type of molecules. The fluorescence emission spectra of the two red light materials in different organic solvents are tested, and the 3,4 is the fluorescence spectra of DP-BTD-CN molecules and DP-BTD-TPE molecules in different solvents respectively. In FIG. 3, the abscissa is the wavelength and the ordinate is the standard light intensity, and the curves in FIG. 3 are spectra in the direction of the arrows in CH (cyclohexane), TOL (toluene), THF (tetrahydrofuran), DCM (dichloromethane), DMF (dimethylformamide) and DMSO (dimethylsulfoxide). In FIG. 4, the abscissa is the wavelength and the ordinate is the standard intensity, and the curves in FIG. 4 are spectra in TOL (toluene), THF (tetrahydrofuran), DCM (dichloromethane), DMF (dimethylformamide) and DMSO (dimethylsulfoxide) in the direction of the arrows. As can be seen from FIGS. 3-4, the fluorescence spectra of DP-BTD-CN and DP-BTD-TPE are significantly red-shifted with increasing polarity of the solvent, and the maximum emission wavelength of DP-BTD-CN is red-shifted by 88nm, indicating that the excited state of the molecule is influenced by the solvent and has Intramolecular Charge Transfer (ICT) property.

2. The red-emitting materials prepared in examples 1 and 2 were tested for their aggregation-induced emission properties

FIG. 5 shows DMSO/H of DP-BTD-CN molecules (prepared from example 1) at different volume fractions of water ₂ Fluorescence spectrum in O solution. In fig. 5, the abscissa is the wavelength and the ordinate is the intensity, and the curves in fig. 5 are spectra in which the volume of water is 80%, 90%, 0%, 70%, 10%, 30%, 50%, and 60% in the direction of the arrow.

FIG. 6 is a graph of the change in fluorescence intensity of DP-BTD-CN molecules (prepared in example 1) in different volume fractions of water. In fig. 6, the abscissa is the volume fraction of water, and the ordinate is the fluorescence intensity.

FIG. 7 shows DMSO/H in different volume fractions of water for DP-BTD-TPE molecules (prepared in example 2) ₂ Fluorescence spectrum in O solution; in fig. 7, the abscissa is the wavelength and the ordinate is the intensity, and the curve in fig. 7 is a spectrum diagram in the direction of the arrow in the order of 50%, 70%, 90%, 30%, 0%, 10% and 20% of the volume of water.

FIG. 8 is a graph showing the change in fluorescence intensity of DP-BTD-TPE molecules (prepared in example 2) in different volume fractions of water. In fig. 8, the abscissa is the volume fraction of water, and the ordinate is the fluorescence intensity.

As can be seen from FIGS. 6 to 8, the fluorescence intensity of the compound gradually increased after decreasing with the increase of the proportion of the poor solvent water, indicating that the molecule has aggregation-induced emission properties.

3. Application of red light material prepared in examples 1 and 2 in fluorescence sensing

(1) Test Red Material Pair F ^- Selectivity and sensitivity of

The prepared red light materials prepared in example 1 and example 2 were prepared into detection solutions (2.0X 10) ^-5 mol/L), respectively testing initial ultraviolet and fluorescence spectra under the excitation wavelength of 365nm, and then respectively adding different anions ((AcO) ^- 、NO ₃ ^- ，HSO ₄ ^- ，H ₂ PO ₄ ^- ，Br ^- ，Cl ^- ，I ^- ) And F) and ^- and testing ultraviolet and fluorescence spectra. The DP-BTD-CN solution presents red light, the color of the solution is obviously changed into blue after F-is added, and the solution is still red after other anions are added.

FIG. 9 is a graph of fluorescence spectra of the red-emitting material (DP-BTD-CN) prepared in example 1 with different anions added, wherein the abscissa is wavelength and the ordinate is light intensity. As can be seen from FIG. 9, different anions (AcO) were added to the DP-BTD-CN solution ^- 、NO ₃ ^- ，HSO ₄ ^- ，H ₂ PO ₄ ^- ，Br ^- ，Cl ^- ，I ^- ) After that, the fluorescence spectrum did not change significantly, but F was added ^- And then, the color of the solution is changed, and the fluorescence spectrum is obviously quenched, which shows that the F-can be selectively detected.

FIG. 10 is a graph showing UV-VIS absorption spectra of the red-emitting material (DP-BTD-TPE) prepared in example 2 with different anions, wherein the abscissa is wavelength and the ordinate is light intensity. FIG. 11 is a fluorescence spectrum of the red-light material prepared in example 2 with different anions added, wherein the abscissa is wavelength and the ordinate is light intensity. As can be seen from FIGS. 10 and 11, the DP-BTD-TPE solution (10) ^-4 mol/L) addition of different anions (AcO) ^- 、NO ₃ ^- ，HSO ₄ ^- ，H ₂ PO ₄ ^- ，Br ^- ，Cl ^- ，I ^- ) And then, an ultraviolet visible absorption spectrogram and a fluorescence spectrogram do not change obviously, but the ultraviolet spectrum changes obviously after the F-is added, and the fluorescence spectrogram is quenched obviously, so that the selective detection of the F-can be realized.

(2) Testing selectivity and sensitivity of red light material to explosive

The red light material of example 1 was formulated into a solution (DMSO/H) ₂ O = 2:8) respectively tested for their initial fluorescence spectra at an excitation wavelength of 365nm, after which the different nitro-explosives (9 × 10) were added respectively ^-5 mol/L), detecting the fluorescence spectrum of the added different nitro explosives, and testing the selectivity of the nitro explosives.

FIG. 12 shows that the red-light material prepared in example 1 can detect different nitro-explosives (9X 10) ^-5 mol/L), wherein the abscissa is wavelength, the ordinate is fluorescence intensity, the curves in FIG. 12 are blank in the direction of the arrow, and the fluorescence spectra of NT (p-nitrotoluene), NB (nitrobenzene), TNT (2,4,6-trinitrotoluene), NP (p-nitrophenol), DNP (2,4-dinitrophenol) and TNP (2,4,6-trinitrophenol) are shown in FIG. 12.

FIG. 13 is a graph of the fluorescence titration TNP of the red-light emitting material obtained in example 1, in which the abscissa is the wavelength and the ordinate is the fluorescence intensity, and FIG. 13 shows the dropping concentration of 0 to 9.0X 10 to the red-light emitting material solution obtained in example 1 ^-5 As can be seen from FIG. 13, the fluorescence intensity of TNP at mol/L (i.e., 0-90. Mu.M) decreases with increasing concentration of TNP.

Further combining with the Stem-Volmer theory to calculate the formula Ksv [ C ]]＝I ₀ 1, [ I ] by treatment of different concentrations of TNP ₀ I) -1, wherein I ₀ Is the initial fluorescence intensity, I is the fluorescence intensity after quenching, and linear fitting is carried out on the initial fluorescence intensity and the fluorescence intensity after quenching to obtain a linear equation, and the quenching combination constant Ksv =3.51 × 10 is obtained from the slope ⁴ L/mol; FIG. 14 shows the results of measurement I of the red-emitting material obtained in example 1 ₀ The trend of the/I-1 values with TNP concentration (the upper inset is the fitted curve).

At the same time, its detection limit on TNP was tested. The limit of detection (LOD) refers to the minimum concentration or amount of a test substance that can be detected from a sample by an analytical method within a given degree of reliability, and is calculated by the formula: LOD =3 σ/m; adding TNP with different concentrations into the detection solution to obtain TNP fluorescence quenching curves with different concentrations, and passing through the TNT concentrations [ C ]]And I ₀ -I is plotted, wherein I ₀ As initial fluorescence intensity, I is fluorescence intensity after quenching, and a linear fit is made thereto, FIG. 15 is I at the time of detection using the red-light material obtained in example 1 ₀ And (3) fitting a curve of the relation between the concentration of the I and the concentration of the TNP to obtain a linear equation, wherein the slope of the linear equation is m, simultaneously testing the fluorescence intensity of the blank sample solution without TNT, testing 6 groups, calculating the fluorescence intensity of the highest point of the fluorescence emission wavelength of the 6 groups of data according to a standard deviation formula to obtain the standard deviation sigma of the blank sample, and substituting the obtained m and sigma into a detection limit calculation formula to obtain the detection limit of the TNP.

Wherein the detection limit calculation formula is as follows: LOD =3 a/m and,

wherein K _SV ＝3.51×10 ⁴ L/mol，σ＝12.68，m＝2.42×10 ⁹ ，

Calculating to obtain: LOD =1.57 × 10 ^-8 mol/L。

The red light material of example 2 was prepared into a solution (DMSO/H2O = 6:4), and the initial fluorescence spectra thereof were measured at an excitation wavelength of 365nm, after which different nitro explosives (9 × 10) were added respectively ^-5 mol/L), detecting the fluorescence spectrum of the added different nitro explosives, and testing the selectivity of the nitro explosives.

FIG. 16 shows that the red-light material prepared in example 2 can detect different nitro-explosives (9X 10) ^-5 mol/L), wherein the abscissa is the wavelength and the ordinate is the fluorescence intensity, and the curves in FIG. 16 are fluorescence spectrograms of DP-BTD-TPE (DP-BTD-TPE blank, NT overlaps with DP-BTD-TPE), NB, TNT, NP, DNP, and TNP in the order of the arrow, fromAs can be seen in FIG. 16, the fluorescence spectrum is clearly quenched after the addition of TNP, indicating the selectivity for TNP.

FIG. 17 is a graph of the fluorescence titration TNP of the red-light emitting material obtained in example 2, in which the abscissa is the wavelength and the ordinate is the fluorescence intensity, and FIG. 17 shows the dropping concentration of 0 to 9.0X 10 to the red-light emitting material solution obtained in example 2 ^-5 As can be seen from FIG. 17, the fluorescence intensity of TNP at mol/L (i.e., 0-90. Mu.M) decreases with increasing TNP concentration.

FIG. 18 shows the results of measurement I of the red-emitting material obtained in example 2 ₀ The trend of the/I-1 value with TNP concentration (fitted curve is the upper panel). FIG. 19 shows the results of the detection of red light materials prepared in example 2 ₀ -I fitted curve to TNP concentration.

Calculating a detection limit according to the data, wherein the detection limit calculation formula comprises the following steps: LOD =3 a/m and,

wherein, K _SV ＝4.06×10 ⁴ L/mol，σ＝12.51，m＝7.08×10 ⁹ ，

Calculating to obtain: LOD =5.30 × 10 ^-9 mol/L。

Comprehensively, the following steps are found: the red light material provided by the invention has a good response effect on TNP, has high selectivity, low detection limit and high TNP detection efficiency.

Claims

1. An application of a red light material in detecting 2,4,6-trinitrophenol is characterized in that the structural formula of the red light material is a compound shown as a formula (8) or a formula (9),