CN110862393B - Perylene diimide bromine substitute, method for preparing bacillus anthracis marker gas-phase sensing film based on perylene diimide bromine substitute and application of perylene diimide bromine substitute - Google Patents
Perylene diimide bromine substitute, method for preparing bacillus anthracis marker gas-phase sensing film based on perylene diimide bromine substitute and application of perylene diimide bromine substitute Download PDFInfo
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Abstract
The invention discloses a perylene diimide bromine substitute, and a method and application for preparing a bacillus anthracis marker gas-phase sensing film based on the perylene diimide bromine substitute, and belongs to the technical field of organic semiconductor materials. The sensor film mainly comprises an organic active assembly material, wherein the organic active material is perylene diimide bromide PBI-1Br, PBI-2Br, PBI-3Br and PBI-4Br, and is loaded on glass, silica gel or a porous anodic alumina substrate by a solution drop coating technology, and the coating concentration is 0.1-0.5 uL/cm 2 . The pyridine diacid sensor is convenient to prepare, simple to operate, obvious in distinguishing and detecting effect on pyridine and derivatives thereof, and the lowest detection limit of the sensing intensity of gas-phase pyridine diacid can reach 2.8 ppt. In addition, the pyridine and the derivative sensor thereof have high stability and quick response time.
Description
Technical Field
The invention belongs to the technical field of organic semiconductor materials, and particularly relates to a perylene diimide bromine substitute, and a method for preparing a bacillus anthracis marker gas-phase sensing film based on the perylene diimide bromine substitute and application of the perylene diimide bromine substitute.
Background
Anthrax is a rod-shaped gram-positive bacillus that causes anthrax, which in turn causes fatal infection of living organisms. In the normal period, bacterial spores can survive in a harsh environment, such as high temperature, freezing, ultraviolet light, dryness, strong acid, and the like. Aspergillus niger spores can be converted into the active form when ambient environmental conditions are favorable. There is a fatal risk if the treatment is not effective within 24-48 hours after the infection of bacillus anthracis. Thus, bacillus anthracis has attracted widespread attention worldwide as a potential biological warfare agent. Rapid and sensitive detection of bacillus anthracis is critical to reducing anthrax infection and preventing bioterrorism. Over the past few decades, there have been many sensitive, accurate and selective detection methods, including biological methods, high pressure liquid chromatography, electrochemical detection methods, among which optical methods are Polymerase Chain Reaction (PCR), Surface Enhanced Raman Spectroscopy (SERS), immunoassay, etc. It is based primarily on the detection of dipicolinic acid, which is about 5-15% of the dry weight of Bacillus anthracis, and is used as a Bacillus anthracis biomarker.
However, not only do current methods of anthrax detection require complex analytical instruments, but these instruments are time consuming and not portable. More importantly, the conventional detection means is only used for detecting the dipicolinate in water, and the detection method for gas-phase dipicolinate is few. Therefore, the dipicolinic acid is used as an important biomarker in the high-lethal bacillus anthracis, and the realization of the rapid, sensitive and high-selectivity gas phase detection of the dipicolinic acid is of great significance to the reduction of anthrax infection and the prevention of bioterrorism.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a perylene diimide bromine substitute, and a method and application for preparing a bacillus anthracis marker gas-phase sensing film based on the perylene diimide bromine substitute.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a perylene diimide bromine substituent, the structure of which is shown as the following formula:
the invention also discloses application of the perylene diimide bromine substitute in preparation of the bacillus anthracis marker gas-phase sensor.
Preferably, the bacillus anthracis marker is dipicolinate.
The invention also discloses a method for preparing a gas-phase sensing film by adopting the perylene diimide bromine substitute, which comprises the following steps:
1) preparing a perylene diimide bromine substituent assembly structure:
taking perylene diimide bromine substitute, adding good solvent to prepare the solution with the concentration of 1 multiplied by 10 -5 ～1×10 -4 A perylene diimide bromine substituent solution in mol/L;
taking the perylene diimide bromine substituent solution, dropwise adding a poor solvent into the solution, standing for 1-3 hours to obtain a perylene diimide bromine substituent assembly structure, and standing, sealing and storing for later use;
2) preparing a perylene diimide bromine substituent sensing film:
uniformly coating the perylene diimide bromide substituent assembly structure on a matrix, standing at room temperature for 1-2 hours, drying, sealing and storing to obtain the perylene diimide bromide substituent sensing film.
Preferably, in step 1), the good solvent is chloroform, dichloromethane or toluene; the poor solvent is methanol, ethanol or n-hexane.
Preferably, in the step 1), the volume ratio of the perylene diimide bromide substituent solution to the poor solvent is 1: 2.
Preferably, in step 2), the substrate is a glass substrate, a silica gel plate substrate or a porous anodized aluminum substrate.
Preferably, in the step 2), the coating volume is 0.1-0.5 uL/cm 2 。
Preferably, in the step 2), the drying treatment is drying for 12-24 hours in a vacuum drying oven under 3000Pa pressure and at 40-60 ℃.
The invention also discloses the perylene diimide bromine substituent gas-phase sensing film prepared by the method.
Compared with the prior art, the invention has the following beneficial effects:
according to the perylene diimide bromine substitute disclosed by the invention, bromine atoms are modified at bay position of perylene diimide, so that the interaction between the bromine atoms and nitrogen atoms in pyridine diacid can be effectively increased, and the sensing detection of gas-phase pyridine diacid is realized through weak interaction between nitrogen and halogen, and the advantages of the perylene diimide bromine substitute are mainly reflected in that:
firstly, the selectivity is high, and the differential detection can be realized by different response conditions of pyridine and derivatives thereof, such as (2-methylpyridine, 3-methylpyridine and 4-methylpyridine);
secondly, the lowest detection limit is extremely low, and the pyridine diacid of ppt grade can be tested; the lowest detection limit of the sensing intensity of the gas-phase pyridine diacid can reach 2.8 ppt;
thirdly, the photo-thermal stability is good, and the response intensity is not attenuated after 50 times of sensing tests;
fourthly, the assembly film has high fluorescence emission efficiency and great advantage for realizing high-sensitivity sensing application;
fifth, the response time is fast.
Based on the advantages of the perylene diimide bromine substitute, the perylene diimide bromine substitute can be made into a sensing film, and the device preparation method is simple and convenient to operate, so that the development purpose of miniaturization of a detection instrument is realized.
Drawings
FIG. 1 is a UV spectrum of PBI-1Br, PBI-2Br, PBI-3Br and PBI-4Br molecules;
FIG. 2 is a fluorescence spectrum of PBI-1Br, PBI-2Br, PBI-3Br and PBI-4Br molecules;
FIG. 3 is a graph of the thermal weight loss of PBI-1Br, PBI-2Br, PBI-3Br and PBI-4Br molecules;
FIG. 4 is a cyclic voltammogram of PBI-1Br, PBI-2Br, PBI-3Br and PBI-4Br molecules;
FIG. 5 is a field emission scanning electron microscope image based on PBI-1Br assembly;
FIG. 6 is a scanning electron microscope image of field emission based on PBI-1Br assembly on a porous anodic aluminum oxide substrate;
FIG. 7a is a result of a pyridine derivative differential detection experiment based on sensing of PBI-1Br assembly film on a glass plate;
FIG. 7b shows the result of a differential detection experiment of a PBI-1Br assembly-based thin film on a silica gel plate for sensing pyridine derivatives;
FIG. 7c is a result of a PBI-1Br assembly-based thin film in a porous anodic alumina sensing pyridine derivative discrimination detection experiment;
FIG. 8 shows the results of the PBI-1Br assembly-based thin film sensing experiment on dipicolinic acid on different substrates;
FIG. 9 is a graph of the response intensity versus concentration of a sensor based on PBI-1Br assembly film for pyridine concentrations ranging from 0ppb to 3750 ppm;
FIG. 10 shows the results of a recoverability experiment of a sensor based on a PBI-1Br assembly film.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in 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.
It should be noted that the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover non-exclusive inclusions, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is described in further detail below with reference to the accompanying drawings:
first, preparation example
Example 1: synthesis of PBI-1Br and preparation of pyridine diacid sensor
(1) Synthesis of PBI-1Br molecule:
n, N-diisooctylamino-perylene diimide (10mmol, 6.15g) was dissolved in 150mL of CH 2 Cl 2 And 34mL of Br was added slowly 2 Stirring at 50 ℃, cooling and refluxing for 48h, removing the flask from the oil bath pot, after the reaction is finished and the temperature is reduced to room temperature, pouring the reaction liquid into a 1000mL beaker, adding 5g of sodium thiosulfate into the mixture system, stirring overnight to remove the unreacted bromine, then carrying out vacuum filtration on the mixture, washing with ultrapure water for three times to obtain dark red solid powder, and drying for 5h at 50 ℃ in a vacuum drying oven. Dissolving the brominated PBI crude product with dichloromethane, adding silica gel for sample mixing, and performing column chromatography for multiple times to obtain perylene diimide monobromide PBI-1Br (0.64 g, the yield is 37.4%).
The corresponding physicochemical identification data are as follows:
PBI-1Br： 1 H NMR(600MHz,CDCl 3 )d(ppm):9.68(d,J＝6Hz,1H,Ar-H),8.80 (s,1H,Ar-H),8.60-8.58(m,3H,Ar-H),8.47-8.45(m,2H,Ar-H),4.18-4.06(m,4H,N- CH 2 -),1.96-1.93(m,2H,-CH-),1.41-1.25(m,16H,-CH 2 -),0.96-0.89(m,12H,CH 3 )； MS(m/s,MALDI-TOP)calcd for C 40 H 42 BrN 2 O 4 [M+H] + 693.23,found 693.61.
the structural formula is as follows:
the UV-visible spectrum is shown in FIG. 1, and PBI-1Br is first prepared at a concentration of 1.0 x 10 -3 mol/L mother liquor, then diluting to 5.0 x 10 -6 mol/L, determined in the wavelength range of 300-700 nm. The ultraviolet-visible absorption spectrum is subjected to normalization treatment, three groups of characteristic absorption peaks of the perylene diimide derivative appear in PBI-1Br, the intensities are sequentially increased, and the three groups of characteristic absorption peaks are respectively assigned as S 0 Electronic state n-0 vibrational level to S 1 Transitions between electronic states n-1, n-2 and n-3 vibrational levels. The maximum absorption peak of PBI-1Br is 524nm, compared with PBI-0Br, the initial absorption wavelength continuously moves towards the long-wave direction, and the obvious red shift and the larger absorption cross section are shown; the fluorescence emission spectrum of PBI-1Br was also investigated as shown in FIG. 2, using 1 x 10 -5 Testing is carried out on the PBI-1Br dichloromethane solution with mol/L concentration, the excitation wavelength is selected to be 460nm, and the emission spectrum of the PBI-1Br is monitored and normalized. PBI-1Br presents two groups of emission peaks in a dichloromethane solvent, and is in mirror symmetry with an ultraviolet visible spectrum. The maximum fluorescence emission peak of PBI-1Br is 544nm, the maximum fluorescence emission peak moves towards the long-wave direction compared with PBI-0Br, and the Stokes displacement of PBI-1Br is 20 nm; the thermogravimetric plot is shown in FIG. 3, and the thermal stability of PBI-0Br and PBI-1Br was tested by thermogravimetric analysis, respectively. The initial thermal cracking temperature (defined as the 5% weight loss temperature) of PBI-0Br was 163 ℃ and the thermal cracking temperature of PBI-1Br was 161 ℃ compared to that without bromine atom substitution, indicating that PBI-1Br had good thermal stability; the cyclic voltammetry curve is shown in fig. 4, a platinum wire is used as a working electrode, silver/silver chloride is used as a reference electrode, a platinum sheet is used as a working counter electrode, tetrabutyl-ammonium hexafluorophosphate is used as an electrolyte to carry out cyclic voltammetry, a reduction peak appears in the reverse scanning process from 0 to-1.5V, the reduction potential of a reference compound PBI-0Br is-0.55V, and the reduction potential of PBI-1Br is-0.51V.
(2) Preparation of sensor film
1) Weighing perylene diimide monobromide substituent PBI-1Br, adding a good solvent to prepare the solution with the concentration of 1 × 10 -5 ～ 1×10 -4 Weighing 1mL of PBI-1Br solution in a 5mL glass bottle, slowly dropwise adding a poor solvent on the solution in a volume ratio of 1:2, standing for 1-3 hours to obtain a perylene PBI-1Br assembly structure, and standing, sealing and storing for later use;
2) respectively and uniformly coating the solution containing the PBI-1Br assembly structure of the perylene diimide monobromo substituent on a substrate, standing at room temperature for 1-2 hours, drying at 40-60 ℃ for 12-24 hours in a vacuum drying oven under 3000Pa, taking out, sealing and storing to obtain the PBI-1Br assembly sensing film. The prepared PBI-1Br assembly structure is characterized by adopting a field emission scanning electron microscope, and the result is shown in figure 5. As can be seen from fig. 5, this system forms a nanofiber structure with a large specific surface. The molecular probe is transferred to the surface of a porous anodic alumina substrate and is characterized by a field emission scanning electron microscope, the result is shown in FIG. 6, and as the molecules to be detected can be rapidly adsorbed to the surface of the film and can penetrate into the film, the detection sensitivity is obviously improved, the balance time is shortened, and better sensing application can be realized.
Example 2: synthesis of PBI-2Br and preparation of pyridine diacid sensor
(1) Synthesis of PBI-2Br molecule:
n, N-diisooctylamino-perylene diimide (10mmol, 6.15g) was dissolved in 150mL of CH 2 Cl 2 And 34mL of Br was added slowly 2 Stirring at 50 ℃, cooling and refluxing for 48h, removing the flask from the oil bath pot, after the reaction is finished and the temperature is reduced to room temperature, pouring the reaction liquid into a 1000mL beaker, adding 5g of sodium thiosulfate into the mixture system, stirring overnight to remove the unreacted bromine, then carrying out vacuum filtration on the mixture, washing with ultrapure water for three times to obtain dark red solid powder, and drying for 5h at 50 ℃ in a vacuum drying oven. Dissolving the brominated PBI crude product with dichloromethane, adding silica gel for sample mixing, and performing column chromatography for multiple times to obtain perylene diimide dibromo-compound PBI-2Br (0.72 g, 41.86%).
The corresponding physicochemical identification data are as follows:
PBI-2Br： 1 H NMR(600MHz,CDCl 3 )d(ppm):9.28-9.26(m,2H,Ar-H),8.74(d, J＝6Hz,2H,Ar-H),8.51-8.48(m,2H,Ar-H),4.15-4.07(m,4H,N-CH 2 -),1.94-1.91(m, 2H,-CH-),1.38-1.32(m,16H,-CH 2 -),0.96-0.80(m,12H,CH 3 )；MS(m/s,MALDI- TOP)calcd for C 40 H 41 Br 2 N 2 O 4 [M+H] + 771.14,found 771.40.
the structural formula is as follows:
the UV-visible spectrum is shown in FIG. 1, and PBI-2Br is first prepared at a concentration of 1.0 x 10 -3 mol/L mother liquor, then diluting to 5.0 x 10 -6 mol/L, determined in the wavelength range of 300-700 nm. The ultraviolet-visible absorption spectrum is subjected to normalization treatment, three groups of characteristic absorption peaks of the perylene diimide derivative appear in PBI-2Br, the intensities are sequentially increased, and the three groups of characteristic absorption peaks are respectively assigned as S 0 Electronic state n-0 vibrational level to S 1 Transitions between electronic states n-1, n-2 and n-3 vibrational levels. The maximum absorption peak of PBI-2Br is 526nm, compared with PBI-0Br, the initial absorption wavelength continuously moves towards the long wave direction, and the obvious red shift and the larger absorption cross section are shown; the fluorescence emission spectrum of PBI-2Br was also investigated as shown in FIG. 2, using 1 x 10 -5 Testing PBI-2Br dichloromethane solution with mol/L concentration, selecting excitation wavelength to be 460nm, monitoring emission spectrum of PBI-1Br and normalizing. PBI-2Br presents two groups of emission peaks in a dichloromethane solvent, and is in mirror symmetry with an ultraviolet visible spectrum. The maximum fluorescence emission peak of PBI-2Br is 549nm, the peak is shifted to the long-wave direction compared with PBI-0Br, and the Stokes shift of PBI-2Br is 23 nm; the thermogravimetric plot is shown in FIG. 3, and the thermal stability of PBI-0Br and PBI-2Br was tested by thermogravimetric analysis, respectively. The initial thermal cracking temperature (defined as the temperature of 5% weight loss) of PBI-0Br is 163 ℃, compared with that of PBI-2Br without bromine atom substitution, the thermal cracking temperature of PBI-2Br is increased to 203 ℃ and increased by 40 ℃, which shows that the introduction of bromine atoms can well improve the thermal stability of PBI derivatives; the cyclic voltammetry curve is shown in fig. 4, a platinum wire is used as a working electrode, silver/silver chloride is used as a reference electrode, a platinum sheet is used as a working counter electrode, tetrabutyl-ammonium hexafluorophosphate is used as an electrolyte to carry out cyclic voltammetry, a reduction peak appears in the reverse scanning process from 0 to-1.5V, the reduction potential of a reference compound PBI-0Br is-0.55V, and the reduction potential of PBI-2Br is-0.44V.
(2) Preparation of sensor film
1) Weighing perylene diimide monobromo substituent PBI-2Br, adding a good solvent to prepare the solution with the concentration of 1 × 10 -5 ～ 1×10 -4 mol/L PBI-2Br solution, 1mL of this solution was weighed in a 5mL glass bottle toSlowly dripping a poor solvent on the perylene core-base composite material in a volume ratio of 1:2, standing for 1-3 hours to obtain a perylene PBI-2Br assembly structure, standing, and storing in a sealed manner for later use;
2) respectively and uniformly coating the solution containing the PBI-2Br assembly structure of the perylene diimide monobromo substituent on a substrate, standing at room temperature for 1-2 hours, drying at 40-60 ℃ for 12-24 hours in a vacuum drying oven under 3000Pa, taking out, sealing and storing to obtain the PBI-2Br assembly sensing film.
Example 3: synthesis of PBI-3Br and preparation of pyridine diacid sensor
(1) Synthesis of PBI-3Br molecule:
n, N-diisooctylamino-perylene diimide (10mmol, 6.15g) was dissolved in 150mL of CH 2 Cl 2 And 34mL of Br was added slowly 2 Stirring at 50 ℃, cooling and refluxing for 48h, removing the flask from the oil bath pot, after the reaction is finished and the temperature is reduced to room temperature, pouring the reaction liquid into a 1000mL beaker, adding 5g of sodium thiosulfate into the mixture system, stirring overnight to remove the unreacted bromine, then carrying out vacuum filtration on the mixture, washing with ultrapure water for three times to obtain dark red solid powder, and drying for 5h at 50 ℃ in a vacuum drying oven. Dissolving the brominated PBI crude product with dichloromethane, adding silica gel for sample mixing, and performing column chromatography for multiple times to obtain perylene diimide tribromide PBI-3Br (0.26 g, 15.11%).
The corresponding physicochemical identification data are as follows:
PBI-3Br： 1 H NMR(600MHz,CDCl 3 )d(ppm):9.43(d,J＝12Hz,1H,Ar-H),8.92 (s,1H,Ar-H),8.83(m,2H),8.71(d,J＝6Hz,1H,Ar-H),4.20-4.10(m,4H,N-CH 2 -), 1.96-1.94(m,2H,-CH-),1.41-1.33(m,16H,-CH 2 -),0.97-0.90(m,12H,CH 3 )；MS(m/s, MALDI-TOP)calcd for C 40 H 40 Br 3 N 2 O 4 [M+H] + 849.05,found 849.45.
the structural formula is as follows:
the UV-visible spectrum is shown in FIG. 1, and PBI-3Br is first prepared at a concentration of 1.0 x 10 -3 mol/L mother liquor, then diluting to 5.0 x 10 -6 mol/L, determined in the wavelength range of 300-700 nm. The ultraviolet-visible absorption spectrum is subjected to normalization treatment, three groups of characteristic absorption peaks of the perylene diimide derivative appear in PBI-3Br, the intensities are sequentially increased, and the three groups of characteristic absorption peaks are respectively assigned as S 0 Electronic state of n-0 vibrational level to S 1 Transitions between electronic states n-1, n-2 and n-3 vibrational levels. The maximum absorption peak of PBI-3Br is 528nm, compared with PBI-0Br, the initial absorption wavelength continuously moves to the long wave direction, and the obvious red shift and the larger absorption cross section are shown; the fluorescence emission spectrum of PBI-3Br was also investigated as shown in FIG. 2, using 1 x 10 -5 Testing PBI-3Br dichloromethane solution with mol/L concentration, selecting excitation wavelength to be 460nm, monitoring the emission spectrum of PBI-3Br and normalizing. PBI-3Br presents two groups of emission peaks in a dichloromethane solvent, and is in mirror symmetry with an ultraviolet visible spectrum. The maximum fluorescence emission peak of PBI-3Br is 557nm, the maximum fluorescence emission peak moves towards the long wave direction compared with PBI-0Br, and the Stokes displacement of PBI-3Br is 29 nm; the thermogravimetric plot is shown in FIG. 3, and the thermal stability of PBI-0Br and PBI-3Br was tested by thermogravimetric analysis, respectively. The initial thermal cracking temperature (defined as the temperature of 5% weight loss) of PBI-0Br is 163 ℃, compared with that of PBI-3Br without bromine atom substitution, the thermal cracking temperature of PBI-0Br is raised to 322 ℃, and is raised by 159 ℃, which shows that the introduction of bromine atoms can well improve the thermal stability of PBI derivatives; the cyclic voltammetry curve is shown in fig. 4, a platinum wire is used as a working electrode, silver/silver chloride is used as a reference electrode, a platinum sheet is used as a working counter electrode, tetrabutyl-ammonium hexafluorophosphate is used as an electrolyte to carry out cyclic voltammetry, a reduction peak appears in the reverse scanning process from 0 to-1.5V, the reduction potential of a reference compound PBI-0Br is-0.55V, and the reduction potential of PBI-3Br is-0.38V.
(2) Preparation of sensor film
1) Weighing perylene diimide monobromide substituent PBI-3Br, adding a good solvent to prepare the solution with the concentration of 1 × 10 -5 ～ 1×10 -4 mol/L PBI-3Br solution, weighing 1mL of the solution in a 5mL glass bottle, slowly dropwise adding a poor solvent on the solution according to the volume ratio of 1:2, standing for 1-3 hours to obtain a perylene PBI-3Br assembly structure, and standing, sealing and storing for later use;
2) respectively and uniformly coating the solution containing the PBI-3Br assembly structure of the perylene diimide monobromo substituent on a substrate, standing at room temperature for 1-2 hours, drying at 40-60 ℃ for 12-24 hours in a vacuum drying oven under 3000Pa, taking out, sealing and storing to obtain the PBI-3Br assembly sensing film.
Example 4: synthesis of PBI-4Br and preparation of pyridine diacid sensor
(1) Synthesis of PBI-4Br molecule
N, N-diisooctylamino-perylene diimide (10mmol, 6.15g) was dissolved in 150mL of CH 2 Cl 2 And 34mL of Br was added slowly 2 Stirring at 50 ℃, cooling and refluxing for 48h, removing the flask out of an oil bath pot, after the reaction is finished and the temperature is reduced to room temperature, pouring the reaction liquid into a 1000mL beaker, adding 5g of sodium thiosulfate into the mixture system, stirring overnight to remove unreacted bromine, then carrying out vacuum filtration on the mixture, washing with ultrapure water for three times to obtain dark red solid powder, and drying at 50 ℃ for 5h in a vacuum drying oven. The crude brominated PBI product is dissolved by dichloromethane, silica gel is added for sample mixing, and perylene diimide tetrabromide PBI-4Br (0.14g, 8.14%) is obtained by multiple separation of column chromatography.
The corresponding physicochemical identification data are as follows:
PBI-4Br： 1 H NMR(600MHz,CDCl 3 )d(ppm):8.83(s,4H,Ar-H),4.20-4.11(m, 4H,N-CH 2 -),1.95-1.93(m,2H,-CH-),1.54-1.32(m,16H,-CH 2 -),0.96-0.91(m,12H, CH 3 )；MS(m/s,MALDI-TOP)calcd for C 40 H 39 Br 4 N 2 O 4 [M+H] + 930.96,found 930.48.
the structural formula is as follows:
the UV-visible spectrum is shown in FIG. 1, and PBI-4Br is first prepared at a concentration of 1.0 x 10 -3 mol/L mother liquor, then diluting to 5.0 x 10 -6 mol/L, determined in the wavelength range of 300-700 nm. The ultraviolet-visible absorption spectrum is subjected to normalization treatment, three groups of characteristic absorption peaks of the perylene diimide derivative appear in PBI-4Br, the intensities are sequentially increased, and the three groups of characteristic absorption peaks are respectively assigned as S 0 Electronic state n-0 vibrational level to S 1 Transitions between electronic states n-1, n-2 and n-3 vibrational levels. The maximum absorption peak of PBI-4Br is 529nm, and compared with PBI-0Br, the initial absorption wavelength continuously moves towards the long-wave direction, and the obvious red shift and a larger absorption cross section are shown; the fluorescence emission spectrum of PBI-4Br was also investigated as shown in FIG. 2, using 1 x 10 -5 Testing PBI-4Br dichloromethane solution with mol/L concentration, selecting excitation wavelength to be 460nm, monitoring the emission spectrum of PBI-4Br and normalizing. PBI-4Br presents two groups of emission peaks in methylene dichloride solvent, and presents mirror symmetry with ultraviolet visible spectrum. The maximum fluorescence emission peak of PBI-4Br is 566nm, the peak moves to the long wave direction compared with PBI-0Br, and the Stokes shift of PBI-4Br is 37 nm; the thermogravimetric plot is shown in FIG. 3, and the thermal stability of PBI-0Br and PBI-4Br was tested by thermogravimetric analysis, respectively. The initial thermal cracking temperature (defined as the temperature of 5% weight loss) of PBI-0Br is 163 ℃, compared with that of PBI-4Br without bromine atom substitution, the thermal cracking temperature of PBI-4Br is raised to 343 ℃ and is raised by 180 ℃, which shows that the introduction of bromine atoms can well improve the thermal stability of PBI derivatives; the cyclic voltammetry curve is shown in fig. 3, a platinum wire is used as a working electrode, silver/silver chloride is used as a reference electrode, a platinum sheet is used as a working counter electrode, tetrabutyl-ammonium hexafluorophosphate is used as an electrolyte to carry out cyclic voltammetry, a reduction peak appears in the reverse scanning process from 0 to-1.5V, the reduction potential of a reference compound PBI-0Br is-0.55V, and the reduction potential of PBI-4Br is-0.31V.
(2) Preparation of sensor film
1) Weighing perylene diimide monobromide substituent PBI-4Br, adding a good solvent to prepare the solution with the concentration of 1 × 10 -5 ～ 1×10 -4 mol/L PBI-4Br solution, 1mL of this solution was weighed in a 5mL glass bottle and slowly dropped thereon in a volume ratio of 1:2Adding a poor solvent, standing for 1-3 hours to obtain a perylene PBI-4Br assembly structure, standing, sealing and storing for later use;
2) respectively and uniformly coating the solution containing the PBI-4Br assembly structure of the perylene diimide monobromo substituent on a substrate, standing at room temperature for 1-2 hours, drying at 40-60 ℃ for 12-24 hours in a vacuum drying oven under 3000Pa, taking out, sealing and storing to obtain the PBI-4Br assembly sensing film.
Second, experimental effect verification
1. Pyridine and derivative distinguishing and detecting experiment based on PBI-1Br assembly film
In order to detect the distinguishing and detecting capability of the PBI-1Br film sensor on pyridine and derivatives thereof, gases of pyridine, 2-methylpyridine, 3-methylpyridine and 4-methylpyridine are selected for testing, and the gases are all diluted to the concentration of about 350ppm before testing. The response intensity change and the gas recovery time of the thin film device prepared by different substrates are tested by a commercial fluorescence test platform. As shown in FIG. 7a, the response strengths of four compounds, pyridine, 2-methylpyridine, 3-methylpyridine and 4-methylpyridine, tested on the glass substrate thin film device, gradually decreased in the order of 4-methylpyridine (-1263), pyridine (-964), 2-methylpyridine (-825) and 3-methylpyridine (-747). Meanwhile, the time for returning to the initial state after the response is 90% is gradually reduced according to the sequence of 4-methylpyridine (6.44s), 2-methylpyridine (5.63s), 3-methylpyridine (5.38s) and pyridine (2.93 s); as shown in FIG. 7b, the response intensity of four compounds, pyridine, 2-methylpyridine, 3-methylpyridine and 4-methylpyridine, tested in the silica gel plate substrate thin film device, gradually decreased in the order of pyridine (-1783), 2-methylpyridine (-744), 4-methylpyridine (-711) and 3-methylpyridine (-397). Meanwhile, the time for returning to the initial state after the response is 90% is gradually reduced according to the sequence of pyridine (82s), 3-methylpyridine (63s), 4-methylpyridine (58s) and 2-methylpyridine (57 s); as shown in FIG. 7c, the response intensity of the four compounds pyridine, 2-methylpyridine, 3-methylpyridine and 4-methylpyridine tested on the porous anodized aluminum substrate thin film device gradually decreased in the order of 4-methylpyridine (-2228), pyridine (-2043), 2-methylpyridine (-2002) and 3-methylpyridine (-1724). Meanwhile, the time to return to the initial state by 90% after the response gradually decreases in the order of 3-picoline (7.69s), 4-picoline (5.43s), pyridine (4.44s), and 2-picoline (3.07 s); pyridine, 2-methylpyridine, 3-methylpyridine and 4-methylpyridine can be well distinguished by changing the detection of the response strength and the recovery time of different substrates.
2. Gas-phase pyridine diacid response determination experiment of PBI-1Br assembly on film sensors with different substrates
In order to explore the sensing of gaseous pyridine diacid by a PBI-1Br assembly sensing film device under different substrates, the PBI-1Br assembly sensing film is prepared by selecting different substrates, the response intensity change of the device to the gaseous pyridine diacid is tested, pyridine diacid saturated steam is introduced into a sealing cavity of the film device loaded by different substrates, the response intensity is tested, and the result is shown in figure 9. As can be seen from fig. 9, the thin film device on the porous anodized aluminum substrate can respond well to the saturated dipicolinate vapor, while the glass substrate and the silica gel plate substrate cannot respond well to the saturated dipicolinate vapor, and the minimum detection limit can reach 2.8 ppt. The result shows that the PBI-1Br assembly sensing thin-film device using the porous anodic alumina as the substrate can respond to pyridine diacid saturated steam well, and a new strategy is provided for efficient identification and detection of the bacillus anthracis virus.
3. Recoverability test of PBI-1Br assembly film sensor
The recoverability of the glass substrate prepared thin film device is tested by continuously introducing 10mL of pyridine with the concentration of 375ppm into the sealed cavity through a commercial fluorescence testing platform and then pumping gas away. The results are shown in FIG. 10. As can be seen in fig. 10, the response intensity increased after pyridine was pumped in, but the device response intensity returned to the baseline position after pyridine was pumped out. Thus, it can be proved that the PBI-1Br film sensor is recoverable, and can still stably detect pyridine gas after 50 times of circulation.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (6)
1. The application of the perylene diimide bromine substitute in the preparation of the gas-phase sensor of the bacillus anthracis marker is characterized in that the structure of the perylene diimide bromine substitute is shown as the following formula:
2. the use of claim 1, wherein the Bacillus anthracis marker is dipicolinate.
3. The method for preparing a gas phase sensing film by using the perylene diimide bromine substitute as set forth in claim 1, which is characterized by comprising the following steps:
1) preparing a perylene diimide bromine substituent assembly structure:
taking perylene diimide bromine substitute, adding good solvent to prepare the solution with the concentration of 1 multiplied by 10 -5 ～1×10 -4 A perylene diimide bromine substituent solution in mol/L;
taking the perylene diimide bromine substituent solution, dropwise adding a poor solvent into the solution, standing for 1-3 hours to obtain a perylene diimide bromine substituent assembly structure, and standing, sealing and storing for later use;
the good solvent is chloroform, dichloromethane or toluene; the poor solvent is methanol, ethanol or n-hexane; the volume ratio of the perylene diimide bromine substituent solution to the poor solvent is 1: 2;
2) preparing a perylene diimide bromide substituent sensing film:
uniformly coating the perylene diimide bromide substituent assembly structure on a substrate, standing at room temperature for 1-2 hours, drying, sealing and storing to obtain a perylene diimide bromide substituent sensing film;
the drying treatment is drying for 12-24 hours in a vacuum drying oven under 3000Pa pressure and 40-60 ℃.
4. The method for preparing a perylene diimide bromide substituent gas-phase sensing thin film according to claim 3, wherein in the step 2), the matrix is a glass matrix, a silica gel plate matrix or a porous anodic alumina matrix.
5. The preparation method of the perylene diimide bromine substituent gas phase sensing film according to claim 3, wherein in the step 2), the coating volume is 0.1-0.5 uL/cm 2 。
6. The perylene diimide bromine substituent gas phase sensing film prepared by the method of any one of claims 3 to 5.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104447744A (en) * | 2014-11-18 | 2015-03-25 | 北京航空航天大学 | Perylene diimide derivative, and application thereof in solar cell and preparation method of perylene diimide derivative |
| CN106117301A (en) * | 2016-06-29 | 2016-11-16 | 陕西师范大学 | One class has the fluorescent chemicals of sensing function and the preparation of fluorescence sense film thereof and application to arylamine class pulmonary carcinoma marker |
| CN107698614A (en) * | 2017-08-29 | 2018-02-16 | 陕西师范大学 | A kind of carborane diimide derivative and synthetic method and the sensor array based on it and preparation method and application |
| CN110330497A (en) * | 2019-07-15 | 2019-10-15 | 陕西师范大学 | A kind of dish alkene-diimide derivative and its synthetic method and the Application in Sensing to gas phase volatile aromatics |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104447744A (en) * | 2014-11-18 | 2015-03-25 | 北京航空航天大学 | Perylene diimide derivative, and application thereof in solar cell and preparation method of perylene diimide derivative |
| CN106117301A (en) * | 2016-06-29 | 2016-11-16 | 陕西师范大学 | One class has the fluorescent chemicals of sensing function and the preparation of fluorescence sense film thereof and application to arylamine class pulmonary carcinoma marker |
| CN107698614A (en) * | 2017-08-29 | 2018-02-16 | 陕西师范大学 | A kind of carborane diimide derivative and synthetic method and the sensor array based on it and preparation method and application |
| CN110330497A (en) * | 2019-07-15 | 2019-10-15 | 陕西师范大学 | A kind of dish alkene-diimide derivative and its synthetic method and the Application in Sensing to gas phase volatile aromatics |
Non-Patent Citations (3)
| Title |
|---|
| F. Javier Céspedes-Guirao等.Synthesis and Photoinduced Electron Transfer of Phthalocyanine-Perylenebisimide Pentameric Arrays.《J. Org. Chem.》.2009,第74卷第5874页Scheme 3. * |
| Regioisomers of Perylenediimide_ Synthesis, Photophysical, and Electrochemical Properties;Ashok Keerthi等;《J. Phys. Chem. B》;20120322;第116卷;第5874页Scheme 3 * |
| Screening mercury (II) with selective fluorescent chemosensor;Liheng Feng等;《Sensors and Actuators B》;20060828;第122卷;第600-604页 * |
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