Synchronous photostable co-assembled material arrays and their application in distinguishing various types of explosives

Abstract

The present invention discloses a synchronous photostable co-assembly material array and its application in distinguishing various types of explosives. The fluorescent sensor array is composed of one or more organic fluorescent sensor materials that can perform fluorescence monitoring and distinction on several types of explosives, and each of the organic fluorescent sensor materials is obtained by co-assembly of carbazole derivatives as shown in formula (I) and (II). The fluorescent sensor array of the present invention can perform multiple continuous fluorescence detection and distinction on several types of explosives at the ng level, with high detection and distinction sensitivity, and the structure and operation of the sensor array are simpler. At the same time, the interference of most organic solvents can be eliminated, and it has strong practicality.

Description

Technical Field

[0001] The present invention belongs to the field of fluorescent sensor arrays composed of organic semiconductor fluorescent nanomaterials, and particularly relates to the design, synthesis, and co-assembly of fluorescent sensor arrays based on several semiconductor materials of carbazole molecules, and selectively achieving continuous and multiple accurate distinctions of several types of explosives according to the differences in fluorescence response changes of the fluorescent sensor arrays. Background Art

[0002] Driven by concerns about safety control in the environment, industry and other fields, the fluorescent detection of explosives has made many advances, including successful commercialization in practical applications. Conventional explosives can be roughly divided into the following categories: nitroalkanes (DMNB, NM), nitroaromatic compounds (DNT, TNT), nitroamines (RDX), nitroesters (PETN), black powder (S8), peroxides (TATP), etc. In addition to simple detection, accurate identification of different types of explosives is also crucial. Sensor arrays are widely used as a means of differentiation. This method uses several types of materials to assemble sensor arrays, such as colorimetric sensor arrays, and auxiliary analysis methods. Great progress has been made in distinguishing volatile organic hazards, drugs and other substances. Therefore, sensor arrays can be used as a means to distinguish various types of explosives. The identification of explosive categories based on fluorescent sensor arrays has also been under continuous research.

[0003] The fluorescent sensor array distinguishes explosives based on the fluorescence method. The main principle of the fluorescence method for distinguishing explosives is that the several fluorescent molecular materials that make up the sensor array interact with the explosive molecules to different degrees, causing the fluorescent materials to produce different fluorescence change signals, and then the purpose of distinction is achieved by analyzing the fluorescence signals of different sensor units. First of all, each type of explosive molecule has different chemical properties. For example, nitroaromatic explosives (DNT, TNT) have high vapor pressure and relatively good volatility; the nitro group on the aromatic ring has strong electron-withdrawing ability, which reduces the LUMO energy of the molecule, and the particularity of the aromatic ring. This type of explosive has a strong binding force with the fluorescent molecule and is easy to capture the electrons on the excited state of the fluorescent molecule, causing the material to produce a fluorescence quenching signal. Therefore, this type of explosive is easy to detect and has been studied more. Nitroamine (RDX) and nitroester (PETN) explosives have low vapor pressure, poor volatility, and poor electron-donating ability, so they are relatively difficult to detect. S and peroxide explosive molecules are also difficult to detect because they have no chromophores.

[0004] In recent years, although some breakthroughs have been made in the detection and differentiation of explosives using fluorescent sensor arrays, it still faces huge challenges, such as limited recognition capabilities, low luminescence efficiency of the material itself, resulting in a limited service life of the material, weak signal response after several uses, and inconsistent photostability of sensor array units, which can also lead to false alarms later. In particular, the asynchronous fluorescence intensity decay (i.e., photostability) of the array units not only shortens the life of the sensor array, but also changes in the signal due to long-term use, leading to reliability issues for multiple detections. These issues need to be further strengthened and improved. Summary of the invention

[0005] In order to improve the above technical problems, the present invention provides a co-assembly, wherein the co-assembly comprises carbazole derivatives as shown in formula (I) and (II):

[0006]

[0007] In the formula (I) and formula (II), R1, R2, R4, and R7 are the same or different and are independently selected from -(CH2) x’ -R 8 -R 9 , where x' is 0, 1 or 2, R 8 is an arylene group or a halogenated arylene group, R 9 H, -COOR 10 、-COR 10 , C 2-6 Alkynyl, C≡N or C 3-6 Alkyl, R 10 H, C 1-4 alkyl;

[0008] m is an integer from 3 to 40;

[0009] R3, R5, R6 are the same or different and are independently selected from C 1-10 Straight or branched alkyl, -(CH2) x -R 11 -OR 12 、-(CH2) y -R 11 -R 13 or -(CH2) z -R 13 ,

[0010] Wherein, x is 0, 1 or 2, y is 0, 1 or 2, z is an integer from 1 to 9, R 11 is an arylene group or a halogenated arylene group, R 12 C 1-10 A straight chain or branched alkyl group, R 13 -H, -CHF2, -CF3, C1-10 Straight or branched alkyl, C substituted by CHF2 or CF3 1-10 Straight or branched alkyl, C 3-10 Cycloalkyl, C substituted by CHF2 or CF3 3-10 The cycloalkyl group,

[0011] n is an integer from 1 to 20.

[0012] According to an embodiment of the present invention, the co-assembly is organic-organic co-assembly, which means that two organic substances are co-assembled using intermolecular interactions as connecting forces, such as van der Waals forces, and belongs to supramolecular self-assembly.

[0013] The present invention also provides a fluorescence sensor array, wherein the fluorescence sensor array is composed of more than one organic fluorescence sensor material arranged in sequence, and the organic fluorescence sensor material is obtained by co-assembling carbazole derivatives shown in formula (I) and (II).

[0014] According to the embodiment of the present invention, the organic fluorescent sensing material can perform fluorescence monitoring and differentiation on a variety of explosives.

[0015] Preferably, the fluorescent sensor array of the present invention is composed of 1 to 8 kinds of organic fluorescent sensor materials arranged in sequence.

[0016] According to the embodiment of the present invention, the length of the organic fluorescent sensing material in the fluorescent sensing array is adjustable, and the distance between two adjacent materials is adjustable.

[0017] According to an embodiment of the present invention, in the fluorescent sensor array, the length of each organic fluorescent sensor material is 3 to 20 mm, preferably 8 to 10 mm; the distance between two adjacent organic fluorescent sensor materials is 5 to 50 mm, preferably 15 to 20 mm.

[0018] Further preferably, R1, R2, R4, R7 are the same or different and are independently selected from -(CH2) x’ -R 8 -R 9 , x' is 0 or 1; R 8 is arylene or halogenated arylene (wherein halogen is selected from fluorine, chlorine or bromine), such as halogenated phenylene, arylene, such as phenylene or naphthylene; R 9 -COOR 10 、-COR 10 , C≡N, C 2-6 Alkynyl, R 10 C 1-4 alkyl;

[0019] Also preferably, R1, R2, R4, and R7 are the same or different and are independently selected from one of the following eight groups:

[0020]

[0021] Among them, the upper side is the connection site.

[0022] Preferably, R3, R5, and R6 are the same or different and are independently selected from C 3-10 Straight or branched alkyl, -(CH2) x -R 11 -OR 12 、-(CH2) y -R 11 -R 13 or -(CH2) z -R 13 ;

[0023] Wherein, x is 0, 1 or 2, y is 0, 1 or 2, z is an integer from 2 to 6, R 11 is phenylene or naphthylene or halogenated phenylene, R 12 C 1-10 A straight chain or branched alkyl group, R 13 -H, -CF3, C 1-10 Straight or branched alkyl, or CF3 substituted C 1-10 A straight chain or branched chain alkyl group.

[0024] Preferably, R3, R5, and R6 are the same or different and are independently selected from C 3-10 The branched alkyl group is an asymmetric alkyl group.

[0025] Also preferably, R3, R5, and R6 are the same or different and are independently selected from one of the following groups:

[0026]

[0027]

[0028] In the above groups, the upper side of the structural formula is the attachment site.

[0029] According to an embodiment of the present invention, each organic fluorescent sensing material in the fluorescent sensing array is an organic semiconductor nanowire or microbelt co-assembled from the carbazole derivatives described in formula (I) and (II).

[0030] Furthermore, each organic fluorescent sensing material in the fluorescent sensing array is a porous membrane with a mesh structure formed by self-assembly and weaving of the organic semiconductor nanowires or microbelts.

[0031] The present invention also provides a method for preparing the co-assembly, which comprises the following steps:

[0032] (1) synthesizing the carbazole derivatives represented by the formula (I) and (II), respectively;

[0033]

[0034]

[0035] wherein each substituent is as defined above;

[0036] (2) In a mixture of a good solvent and a poor solvent, the carbazole derivatives represented by formula (I) and (II) in step (1) are mixed and co-assembled to obtain the co-assembled product.

[0037] The present invention also provides a method for preparing the organic fluorescent sensor material, characterized in that the method includes a method for preparing the co-assembly.

[0038] The present invention also provides a method for preparing a fluorescence sensor array, the method comprising the following steps:

[0039] (1) synthesizing the carbazole derivatives represented by the formula (I) and (II), respectively;

[0040]

[0041] wherein each substituent is as defined above;

[0042] (2) in a mixture of a good solvent and a poor solvent, the carbazole derivatives represented by formula (I) and (II) in step (1) are co-assembled to prepare at least one of the organic fluorescent sensing materials,

[0043] (3) The organic fluorescent sensing material obtained in step (2) is applied to different positions inside the same glass tube to obtain the fluorescent sensing array.

[0044] According to an embodiment of the present invention, in step (1): R 1 With R 2 Similarly, to prepare a carbazole derivative wherein m=3 in formula (I), the step (1) specifically comprises:

[0045] (1a) The compound represented by formula (A) and R 3 X' reaction to obtain a compound represented by formula (III);

[0046]

[0047] X in formula (A) and formula (III) is the same or different, and is independently selected from halogen (such as Br, I); X' in RX' is selected from halogen (such as Br, I);

[0048] (1b) The compound shown in formula (III) reacts with R 1 B(OH)2 to obtain the compound shown in formula (IV);

[0049]

[0050] In formula (IV), the definitions of R 1 and X are the same as described above;

[0051] (1c) The compound shown in formula (IV) reacts with bis(pivaloyl)diboron to obtain the compound shown in formula (V);

[0052]

[0053] (1d) The compound shown in formula (IV) reacts with the compound shown in formula (V) to obtain the carbazole derivative shown in formula (I), where n = 3; wherein, the molar ratio of the compound shown in formula (IV) to the compound shown in formula (V) is 2.1:1 to 2.5:1 (such as 2.2:1).

[0054] Those skilled in the art should understand that when R 1 is different from R 2 the method includes at least replacing the substrate in at least one of the above steps with

[0055] According to the embodiments of the present invention, when preparing the carbazole derivative with 3 < m ≤ 40 in formula (I) in step (1), step (1) specifically includes:

[0056] (2a) The compound shown in formula (A') reacts with R 3 X' to obtain the compound shown in formula (III');

[0057]

[0058] X in formula (A') and formula (III') is the same or different, and is independently selected from halogen (such as Br, I); X' in RX' is selected from halogen (such as Br, I); p is an integer from 2 to 38;

[0059] (2b) The compound shown in formula (III) reacts with R 1 B(OH)2 to obtain the compound shown in formula (IV);

[0060]

[0061] In formula (IV), R 1 and R 3 have the meanings as described above;

[0062] (2c) The compound shown in formula (III’) reacts with bis(pinacolato)diboron to obtain the compound shown in formula (VI’);

[0063]

[0064] In formula (VI’), p is an integer from 2 to 38;

[0065] (2d) The compound shown in formula (IV) reacts with the compound shown in formula (VI’) to obtain the carbazole derivative shown in formula (I), where 3 < m ≤ 40; wherein, the molar ratio of the compound shown in formula (IV) to the compound shown in formula (VI’) is 2.1:1 to 2.5:1 (for example, 2.2:1).

[0066] According to the embodiments of the present invention, in step (1), a carbazole derivative with 1 ≤ n ≤ 20 in formula (II) is prepared, where R 4 is the same as R 7 , R 5 is the same as R 6 , and the specific steps of step (1) include:

[0067] (3a) The compound shown in formula (A) reacts with R 5 X” to obtain the compound shown in formula (III”);

[0068]

[0069] X in formula (A) and formula (III”) is the same or different, and are independently selected from halogens (for example, Br, I); X” in RX” is selected from halogens (for example, Br, I); in formula (III”), R 5 has the meaning as described above;

[0070] (3b) The compound shown in formula (III”) reacts with R 4 B(OH)2 to obtain the compound shown in formula (IV”);

[0071]

[0072] In formula (IV”), the definitions of R 4 , R 5 and X are as described above;

[0073] (3c) The compound shown in formula (IV”) reacts with bis(pinacolato)diboron to obtain the compound shown in formula (V”);

[0074]

[0075] (3d) the compound represented by formula (VI") is reacted with the compound represented by formula (V") to obtain the compound represented by formula (II), wherein 1≤n≤20;

[0076]

[0077] The molar ratio of the compound represented by formula (V") to the compound represented by formula (VI") is 1:2.1 to 2.5 (for example, 1:2.2).

[0078] It should be understood by those skilled in the art that R 4 With R 7 Not the same, or R 5 With R 6 When different, the method comprises at least one of the substrates in the above step Replace with

[0079] Preferably, in step (2), the molar ratio of the carbazole derivative represented by formula (I) to the carbazole derivative represented by formula (II) is 10 to 1000:1; for example, it can be 10:1, 20:1, 50:1, 100:1, 200:1, 300:1, 400:1, 500:1, 600:1, 700:1, 800:1, 900:1 or 1000:1.

[0080] Preferably, the step (2) comprises: dissolving the carbazole derivatives represented by formula (I) and (II) obtained in step (1) in a good solvent in proportion, then adding a poor solvent, and standing, and the carbazole derivatives represented by formula (I) and (II) are prepared by co-assembly to obtain a suspension of the organic fluorescent sensing material.

[0081] Preferably, the step (2) further comprises: after the suspension of the several organic fluorescent sensor materials is allowed to stand, the organic fluorescent sensor material at the bottom of the container is taken out, and the organic fluorescent sensor material is placed in a poor solvent again to be evenly dispersed and repeatedly washed to obtain the organic fluorescent sensor material.

[0082] Preferably, the volume ratio (mL:mL) of the good solvent to the poor solvent is 1:3-10.

[0083] Preferably, the good solvent is selected from chloroalkanes and C 2-5 Esters are, for example, dichloromethane, chloroform, 1,2-dichloroethane, ethyl acetate or methyl acetate.

[0084] Preferably, the poor solvent is an alcohol organic solvent or a cycloalkane, such as methanol, ethanol or cyclohexane.

[0085] Preferably, the step (3) comprises: injecting the suspension of the organic fluorescent sensor material obtained in the step (2) into the same quartz tube in sequence, and waiting for the solvent to evaporate to dryness, thereby obtaining the organic fluorescent sensor array.

[0086] The fluorescent sensor array described in the present invention is composed of a porous membrane material with a mesh structure formed by several organic semiconductor nanowires or micron strips. These materials have a high specific surface area and have different fluorescence responses to different explosives. Several types of explosives can be detected and distinguished based on the fluorescence response. At the same time, since these materials are co-assembled, the materials have synchronous photostability decay properties, which can effectively avoid false alarms caused by inconsistent photostability decay of the materials, enhance the durability of the materials, and realize detection and distinction of explosives multiple times.

[0087] The present invention also provides application of the fluorescent sensor array in distinguishing explosives, wherein the fluorescent sensor array is composed of at least one organic fluorescent sensor material.

[0088] According to the embodiment of the present invention, the fluorescence sensor array can perform rapid multiple continuous fluorescence detection and differentiation on explosives.

[0089] According to an embodiment of the present invention, the fluorescence sensor array can be used to rapidly and repeatedly detect and distinguish solid explosives through continuous fluorescence.

[0090] According to an embodiment of the present invention, the fluorescent sensor array can be used to detect and differentiate trace amounts of explosives, where the trace amounts are at the ng or sub-ng level.

[0091] In the present invention, when the fluorescent sensor array contacts with trace explosive vapor (the explosive is preferably solid), since each organic fluorescent sensor material has different substituted functional group side chains and different morphologies, and different surface physical and chemical properties, different forms of fluorescence changes will occur, thereby affecting the FRET process between molecules and causing changes in fluorescence signals. By analyzing the signals of these fluorescence changes, it can be used to actually realize rapid multiple continuous fluorescence detection and differentiation of several types of explosives.

[0092] The obtained different organic fluorescent sensing materials are spin-coated in a quartz tube, and the vapor concentration of the explosive is increased by placing the explosive in a heating gun and setting different temperatures. When different explosive vapors come into contact with organic fluorescent sensing materials with different substituted functional group side chains, the fluorescence of the different fluorescent sensing materials will change in different forms. By analyzing the fluorescence change signal, rapid and multiple continuous fluorescence detection and differentiation of the explosives can be achieved.

[0093] According to an embodiment of the present invention, the explosive is selected from at least one of RDX, trinitrotoluene (TNT), pentaerythritol tetranitrate (PETN), ammonium nitrate (AN), black powder (S) and nitromethane (NM).

[0094] The main body of the constituent materials of the fluorescent sensor array of the present invention is formed by co-assembly of two typical P-type semiconductor fluorescent sensor materials. The present invention modifies the substituted functional groups and polymerization degree of the main body. When the organic fluorescent sensor material interacts with the high-temperature steam of the explosive containing nitro group, different degrees of electron transfer or physical adsorption of different strengths will occur, causing different forms of fluorescence changes of several organic fluorescent sensor materials. The fluorescence response of material 1 is named Q1, the fluorescence response of material 2 is named Q2, and the fluorescence response of material N is named QN. The different forms of fluorescence change arrays obtained in this way are different and unique to each type of explosive. Therefore, this sensor array composed of several different organic fluorescent sensor materials can realize rapid multiple continuous fluorescence detection and distinction of several types of explosives.

[0095] In the present invention, the explosives are classified according to categories, and one category of explosives may contain one or more explosives.

[0096] Beneficial effects of the present invention

[0097] (1) The organic fluorescent sensing material of the present invention is formed by co-assembling two P-type organic semiconductor fluorescent sensing materials. Such materials can solve the problems of poor stability and low luminous efficiency when using the compound of formula (I) alone and poor detection sensitivity when using the compound of formula (II) alone. Specifically, the emission spectrum of the aggregate of formula (I) overlaps with the absorption spectrum of the monomer of formula (II), which can generate fluorescence resonance energy transfer (FRET). In the present invention, the energy of the compound represented by formula (I) is transferred to the compound represented by formula (II), so that the compound represented by formula (II) emits fluorescence, thereby inhibiting the photooxidation reaction, enhancing the photostability of the material, and improving the luminescence efficiency of the material. At the same time, since the luminescence of the material is emitted by formula (II), the decay process of the photostability of several types of array molecules is synchronized.

[0098] (2) The organic fluorescent sensing material used in the present invention is obtained by co-assembly of two types of carbazole derivatives. By modifying the side chains and polymerization degree of specific substituted functional groups on the main body and co-assembling with molecules with strong photostability, different forms of fluorescence changes can be formed for different explosives, and synchronous changes in photostability can also be achieved. The present invention forms a sensor array by assembling such organic fluorescent sensing materials that have synchronous changes in photostability but different fluorescence changes for explosives, thereby forming a fluorescence change array unique to each type of explosive and achieving multiple continuous fluorescence detection and differentiation of several types of explosives.

[0099] (3) The fluorescent sensor array of the present invention can perform multiple continuous fluorescence detection and differentiation of several types of explosives at the ng level, with high detection and differentiation sensitivity, and the sensor array is simpler to construct and operate, and can also eliminate the interference of most organic solvents, and has strong practicality. After design, this sensor array can be further made into a portable device that can quickly detect and differentiate several types of explosives, and applied and serve the society. This is a work of great significance and has far-reaching application and development prospects.

[0100] (4) The present invention also provides a simple and efficient method for preparing several organic fluorescent sensing materials in the sensor array. The synthesis route of the method is simple and convenient for large-scale preparation. The nanowire or microbelt growth method is simple and fast.

[0101] Definition and explanation of terms

[0102] “C 1-10 The term "straight or branched alkyl" refers to straight or branched alkyl groups having 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. 1-6 The term "alkyl" refers to straight-chain and branched alkyl groups having 1, 2, 3, 4, 5 or 6 carbon atoms. The alkyl group is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl or 1,2-dimethylbutyl, or the like or isomers thereof.

[0103] The term "aryl" is understood to mean preferably a monovalent aromatic or partially aromatic monocyclic, bicyclic or tricyclic hydrocarbon ring having 6 to 20 carbon atoms, preferably "C 6-14 The term "C 6-14The term "aryl" is understood to mean preferably a monovalent aromatic or partially aromatic monocyclic, bicyclic or tricyclic hydrocarbon ring ("C 6-14 or a ring having 9 carbon atoms ("C9 aryl"), for example indanyl or indenyl, or a ring having 10 carbon atoms ("C 10 aryl), such as tetrahydronaphthyl, dihydronaphthyl or naphthyl, or a ring having 13 carbon atoms ("C 13 aryl), such as fluorenyl, or a ring having 14 carbon atoms ("C 14 "aryl"), for example anthracenyl.

[0104] The term "arylene" refers to a group corresponding to the above term with one additional substitution site.

[0105] The term "C 2-6 "Alkynyl" is understood to mean preferably a straight-chain or branched monovalent hydrocarbon radical which contains one or more triple bonds and has 2, 3, 4, 5 or 6 carbon atoms, for example 2 or 3 carbon atoms ("C 2-3 The alkynyl group is, for example, ethynyl, prop-1-ynyl, prop-2-ynyl, but-1-ynyl, but-2-ynyl, but-3-ynyl, pent-1-ynyl, pent-2-ynyl, pent-3-ynyl, pent-4-ynyl, hex-1-ynyl, hex-2-ynyl, hex-3-ynyl, hex-4-ynyl, hex-5-ynyl, 1-methylprop-2-ynyl, 2-methylbut-3-ynyl, 1-methylbut-3-ynyl, 1-methylbut-2-ynyl, 3-methylbut-1-ynyl, 1-ethylprop-2-ynyl, 3-methylpent-4-ynyl, 2-methyl pent-4-ynyl, 1-methylpent-4-ynyl, 2-methylpent-3-ynyl, 1-methylpent-3-ynyl, 4-methylpent-2-ynyl, 1-methylpent-2-ynyl, 4-methylpent-1-ynyl, 3-methylpent-1-ynyl, 2-ethylbut-3-ynyl, 1-ethylbut-3-ynyl, 1-ethylbut-2-ynyl, 1-propylprop-2-ynyl, 1-isopropylprop-2-ynyl, 2,2-dimethylbut-3-ynyl, 1,1-dimethylbut-3-ynyl, 1,1-dimethylbut-2-ynyl or 3,3-dimethylbut-1-ynyl.

[0106] The term "C 3-10 The term "cycloalkyl" is understood to mean a saturated monovalent monocyclic, bicyclic hydrocarbon ring or a bridged cycloalkane having 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. 3-10The cycloalkyl group may be a monocyclic hydrocarbon group, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclodecyl, or a bicyclic hydrocarbon group such as decalin. The cycloalkyl group may be a spiro ring, such as spiro [3,3] ring, spiro [3,4] ring, spiro [3,5] ring, spiro [4,4] ring, spiro [4,5] ring, spiro [5,5] ring. BRIEF DESCRIPTION OF THE DRAWINGS

[0107] Figure 1 This is the NMR data spectrum of compound I-1 of Example 1 of the present invention.

[0108] Figure 2 This is a mass spectrum data diagram of compound I-1 of Example 1 of the present invention.

[0109] Figure 3 The SEM image of the self-assembled aggregate of compound I-1 of Example 1 of the present invention is

[0110] Figure 4 This is the NMR data spectrum of compound I-2 of Example 2 of the present invention.

[0111] Figure 5 This is a mass spectrum data diagram of compound I-2 of Example 2 of the present invention.

[0112] Figure 6 The SEM image of the self-assembled aggregate of compound I-2 of Example 2 of the present invention is

[0113] Figure 7 This is the NMR data spectrum of compound II-1 of Example 3 of the present invention.

[0114] Figure 8 This is the mass spectrum data of compound II-1 of Example 3 of the present invention.

[0115] Fig. 9 This is a SEM image of the fluorescent sensor array in Example 4-5 of the present invention.

[0116] Fig.10 This is a photostability test of the fluorescent sensor array in Examples 4-5 and the self-assembled fluorescent sensor material in Examples 1-2.

[0117] Fig.11 Graph showing the fluorescence curves of the fluorescence sensor array in Example 6 of the present invention for different concentrations of TNT.

[0118] Fig.12 This is a fluorescence curve diagram of the fluorescent photosensitive material for detecting S8 in Example 7 of the present invention.

[0119] Fig.13 This is a fluorescence curve diagram of the fluorescent photosensitivity material in Example 8 of the present invention for detecting RDX.

[0120] Fig.14 This is a fluorescence curve diagram of the fluorescent photosensitive material in Example 9 of the present invention detecting PETN.

[0121] Fig.15 This is a fluorescence curve diagram of the fluorescent photosensitivity material for detecting AN in Example 10 of the present invention.

[0122] Fig.16 This is a fluorescence curve diagram of the fluorescent photosensitizing material for detecting NM in Example 11 of the present invention.

[0123] Fig.17 This is a distribution point diagram of the fluorescent photosensitive material used in Example 12 of the present invention to distinguish various types of explosives. DETAILED DESCRIPTION

[0124] The technical scheme of the present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only exemplary descriptions and explanations of the present invention and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are included in the scope that the present invention is intended to protect.

[0125] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0126] Example 1

[0127] Compound I-1 was prepared by the following method:

[0128]

[0129] (1) 2 g of 2,7-dibromocarbazole was dissolved in 30 ml of N,N-dimethylformamide (DMF) solution, and the solution was placed in an ice bath at 0°C. 1.2 equivalents of 148 mg of sodium hydride solid were slowly added. After continuous stirring for half an hour, 1.5 equivalents of 1-bromooctane were slowly added. After reacting at room temperature overnight, the product was obtained by column chromatography.

[0130] (2) 0.5 g of the product obtained in step (1) was added to 20 mL of 1,4-dioxane solution, and 3 equivalents of bis(pentanoyl)diboron, 3 equivalents of potassium acetate, and 5% equivalents of [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride were added. The mixture was reacted at 80° C. under argon protection for 8 hours, and the product was obtained by column chromatography.

[0131] (3) 0.5 g of the product obtained in step (1) was dissolved in 20 mL of 1,4-dioxane solution, and 0.9 equivalent of p-methylcarbonylphenylboronic acid, 5% equivalent of tetrakis(triphenylphosphine)palladium, and 3 equivalents of potassium carbonate were added. The mixture was reacted at 80° C. under argon protection for 8 hours, and the product was obtained by column chromatography.

[0132] (4) 1.5 mmol and 3.3 mmol of the product obtained in step (2) and step (3) were respectively added to 20 mL of 1,4-dioxane solution, 5% tetrakis(triphenylphosphine)palladium and 3 equivalents of potassium carbonate were added, and the reaction was carried out overnight at 80° C. under argon protection. The product (molecule I-1) was obtained by column chromatography; its nuclear magnetic resonance data is shown in the figure Figure 1 As shown; mass spectrum data as shown Figure 2 shown.

[0133] (5) dissolving the molecule I-1 obtained in step (4) in a good solvent and then adding a poor solvent, wherein the good solvent is chloroform and the poor solvent is methanol, and the volume ratio of the good solvent to the poor solvent is 1:10; allowing the mixture to stand, and the carbazole derivative with p-methylcarbonylbenzene self-assembles to obtain a suspension of organic semiconductor nanowires having different fluorescence responses to several types of explosives.

[0134] like Figure 3 As shown, after compound I-1 aggregates, it gradually self-assembles into nanowire aggregates through π-π interactions in a poor solvent.

[0135] A small amount of aggregates was placed in an instrument for measuring fluorescence quantum yield, and the excitation wavelength was selected as 385 nanometers. The fluorescence quantum yield was detected to be 47%.

[0136] Wherein, the determination method of the above-mentioned fluorescence quantum yield is:

[0137] Drop the nanowire aggregate on a quartz plate, and select the best excitation wavelength by measuring the fluorescence excitation spectrum of the sample. The instrument model is Hamamatsu C11247 fluorescence quantum yield. The test selects the single wavelength scanning mode, and measures the sample fluorescence quantum yield at the best excitation wavelength. Each sample is dropped on 3 membranes for parallel testing and the average is taken.

[0138] Example 2

[0139] Compound I-2 was prepared by the following method:

[0140]

[0141] (1) Dissolve 2 g of 2,7-dibromocarbazole in 30 ml of N,N-dimethylformamide (DMF) solution, place the solution in an ice bath at 0°C, slowly add 1.2 equivalents of 148 mg of sodium hydride solid, continue stirring for half an hour, then slowly add 1.5 equivalents of 1-bromohexane, react at room temperature overnight, and obtain the product by column chromatography.

[0142] (2) 0.5 g of the product obtained in step (1) was added to 20 mL of 1,4-dioxane solution, and 3 equivalents of bis(pentanoyl)diboron, 3 equivalents of potassium acetate, and 5% equivalents of [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride were added. The mixture was reacted at 80° C. under argon protection for 8 hours, and the product was obtained by column chromatography.

[0143] (3) 0.5 g of the product obtained in step (1) was dissolved in 20 mL of 1,4-dioxane solution, and 0.9 equivalent of p-cyanophenylboronic acid, 5% equivalent of tetrakis(triphenylphosphine)palladium, and 3 equivalents of potassium carbonate were added. The mixture was reacted at 80° C. under argon protection for 8 hours, and the product was obtained by column chromatography.

[0144] (4) 1.5 mmol and 3.3 mmol of the product obtained in step (2) and step (3) were respectively added to 20 mL of 1,4-dioxane solution, 5% tetrakis(triphenylphosphine)palladium and 3 equivalents of potassium carbonate were added, and the mixture was reacted overnight at 80° C. under argon protection. The product (molecule I-2) was obtained by column chromatography; its nuclear magnetic resonance data is shown in the figure below: Figure 4 As shown; mass spectrum data as shown Figure 5 shown.

[0145] (5) dissolving the molecule I-2 obtained in step (4) in a good solvent and then adding a poor solvent, wherein the good solvent is chloroform and the poor solvent is methanol, and the volume ratio of the good solvent to the poor solvent is 1:10; allowing the mixture to stand, and the carbazole derivative with p-cyanobenzene self-assembles to obtain a suspension of organic semiconductor microbelts having different fluorescence responses to several types of explosives.

[0146] like Figure 6 As shown, after aggregation, compound I-2 gradually self-assembles into microribbon aggregates through π-π interactions in a poor solvent.

[0147] A small amount of aggregates was placed in an instrument for measuring fluorescence quantum yield, and the excitation wavelength was selected as 385 nanometers. The fluorescence quantum yield was detected to be 26%.

[0148] Wherein, the determination method of the above-mentioned fluorescence quantum yield is:

[0149] Drop the micron ribbon aggregate on the quartz plate, and select the best excitation wavelength by measuring the fluorescence excitation spectrum of the sample. The instrument model is Hamamatsu C11247 fluorescence quantum yield. The test selects the single wavelength scanning mode, and measures the sample fluorescence quantum yield at the best excitation wavelength. Each sample is dropped on 3 membranes for parallel testing and the average is taken.

[0150] Example 3

[0151] Compound II-1 was prepared by the following method:

[0152]

[0153] (1) 2 g of 2,7-dibromocarbazole was dissolved in 30 ml of N,N-dimethylformamide (DMF) solution, and the solution was placed in an ice bath at 0°C. 1.2 equivalents of 148 mg of sodium hydride solid were slowly added. After continuous stirring for half an hour, 1.5 equivalents of 1-bromooctane were slowly added. After reacting at room temperature overnight, the product was obtained by column chromatography.

[0154] (2) 0.5 g of the product obtained in step (1) was dissolved in 20 mL of 1,4-dioxane solution, and 0.9 equivalent of p-cyanophenylboronic acid, 5% equivalent of tetrakis(triphenylphosphine)palladium, and 3 equivalents of potassium carbonate were added. The mixture was reacted at 80° C. under argon protection for 8 hours, and the product was obtained by column chromatography.

[0155] (3) 0.3 g of the product obtained in step (2) was dissolved in 20 mL of 1,4-dioxane solution, and 1.2 equivalents of bis(pentanoyl)diboron, 3 equivalents of potassium acetate, and 5% equivalents of [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride were added. The mixture was reacted at 80° C. under argon protection for 8 hours, and the product was obtained by column chromatography.

[0156] (4) 1.5 mmol of the product obtained in step (3) and 3.3 mmol of 4,7-dibromo-2,1,3-benzothiadiazole were added to 20 mL of 1,4-dioxane solution, 5% tetrakis(triphenylphosphine)palladium and 3 equivalents of potassium carbonate were added, and the mixture was reacted overnight at 80° C. under argon protection. The product (molecule II-2) was obtained by column chromatography; its nuclear magnetic resonance data is shown in the figure below: Figure 7 As shown; mass spectrum data as shown Figure 8 shown.

[0157] (5) dissolving the molecule II-2 obtained in step (4) in a good solvent and then adding a poor solvent, wherein the good solvent is chloroform and the poor solvent is methanol, and the volume ratio of the good solvent to the poor solvent is 1:10; allowing the mixture to stand, and the carbazole derivative with p-methylcarbonylbenzene self-assembles to obtain a suspension of organic semiconductor nanowires having different fluorescence responses to several types of explosives.

[0158] Example 4

[0159] Compound I-1 in Example 1 and compound II-1 in Example 3 are dissolved in a good solvent at a molar ratio of 500:1, and then a poor solvent is added, wherein the good solvent is chloroform, the poor solvent is methanol, and the volume ratio of the good solvent to the poor solvent is 1:10; the mixture is allowed to stand, and the two types of carbazole derivatives with different substituents are co-assembled to obtain a suspension of organic semiconductor nanowires or microbelts with different fluorescence responses to several types of explosives. After the obtained suspension is allowed to stand for several hours, the film at the bottom of the container is taken out and applied to a quartz glass tube to prepare a fluorescent sensor array composed of the carbazole derivatives shown in formula (I-1) and (II-1) by co-assembly.

[0160] Example 5

[0161] Compound I-2 in Example 2 and compound II-1 in Example 3 are dissolved in a good solvent at a molar ratio of 500:1, and then a poor solvent is added, wherein the good solvent is chloroform and the poor solvent is methanol, and the volume ratio of the good solvent to the poor solvent is 1:10; the mixture is allowed to stand, and the two types of carbazole derivatives with different substituents are co-assembled to obtain a suspension aggregate of organic semiconductor nanowires or microbelts with different fluorescence responses to several types of explosives. After the obtained suspension is allowed to stand for several hours, the film at the bottom of the container is taken out and applied to a quartz glass tube to prepare a fluorescent sensor array composed of the carbazole derivatives shown in formula (I-2) and (II-1) through co-assembly.

[0162] The SEM images of the fluorescent sensor arrays prepared in Example 4 and Example 5 are as follows: Fig. 9 As shown, Fig. 9 The left picture represents Example 4, Fig. 9 The right picture represents Example 5.

[0163] like Fig.10 As shown, the fluorescent sensing material obtained by self-assembly of compound I-1 in Example 1 and compound I-2 in Example 2 (i.e., respectively Fig.10 After continuous illumination for 1 hour, the fluorescence intensity of the middle molecules I-1 and I-2 decreased by 60 and 75%, respectively (see Fig.10 Left figure); the organic fluorescent sensor materials (i.e., the fluorescent sensor arrays in Examples 4 and 5) co-assembled with the two molecules and compound II-1, after continuous illumination for 1 hour, the fluorescence intensity only decreased and the changes tended to be synchronized, and the decrease in intensity was only 24%, indicating that after adding compound II-1 for co-assembly, the photostability was greatly improved (see Fig.10 right).

[0164] A small amount of the fluorescence sensor arrays in Example 4 and Example 5 were respectively taken for fluorescence quantum yield test, and the excitation wavelength was selected as 385 nanometers. The fluorescence quantum yields were detected to be 63% and 65% respectively, which greatly improved the luminous efficiency.

[0165] Example 6

[0166] The fluorescent sensor arrays obtained in Example 4 and Example 5 were excited by a 385 nm excitation light source. Using a solid explosive detector, 0.5 ng, 2 ng, and 10 ng of TNT were respectively pipetted into a heating gun, and the heating temperature was set to 170°C. TNT vapor was added to the surface of the membrane for more than dozens of times at each concentration. The test results showed that the materials at both ends showed the following at the three concentrations: Fig.11 fluorescence changes.

[0167] Example 7

[0168] The same method as in Example 6 was used, except that the detected object was replaced with 3 ng sulfur, and dozens of tests were performed (i.e., after the first test was completed, the fluorescent sensing material was used for the second test again, and this was repeated ten times in sequence). The test results showed that at the current concentration, the materials at both ends showed the following Fig.12 fluorescence changes.

[0169] Example 8

[0170] The same method as in Example 6 was used, except that the substance to be detected was replaced with 10 ng RDX, and the detection was performed dozens of times. The detection results showed that at the current concentration, the materials at both ends showed the following Fig.13 fluorescence changes.

[0171] Example 9

[0172] The same method as in Example 6 was used, except that the substance to be detected was replaced with 10 ng PETN, and the detection was performed dozens of times. The detection results showed that at the current concentration, the materials at both ends showed the following Fig.14 fluorescence changes.

[0173] Example 10

[0174] The same method as in Example 6 was used, except that the test substance was changed to 50 ng, 75 ng, and 100 ng AN, and the test was performed dozens of times. The test results at the three concentrations were as follows: Fig.15 fluorescence changes.

[0175] Embodiment 11

[0176] The same method as in Example 6 was used, except that the detected substance was changed to 90ppm, 180ppm, and 360ppm NM, and dozens of tests were performed. The test results at the three concentrations were as follows: Fig.16 fluorescence changes.

[0177] Example 12

[0178] The fluorescence response changes of the fluorescent sensor arrays prepared in Example 4 and Example 5 (referred to as Material 1 and Material 2) to the above six explosives were analyzed graphically. The fluorescence response of Material 1 is named Q1, and the fluorescence response of Material 2 is Q2. According to the ratio analysis of Q1 / Q2 and Q2 / Q1, the fluorescence response changes of the sensor array to each type of explosive are unique, such as Fig.17 The results show that this type of material can be well distinguished after dozens of tests and has good durability.

[0179] Through Figure 11-16 The analysis found that the fluorescence responses of the two materials to AN and NM were different from the other three after fluorescence quenching, so the five types of explosives were distinguished. Therefore, the type of explosive detected can be determined based on the response of the sensor array composed of the two materials.

[0180] The above is an explanation of the embodiments of the present invention. However, the present invention is not limited to the above embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A co-assembly, characterized in that: The co-assembly comprises carbazole derivatives as shown in formula (I) and (II): In the formula (I), R1 and R2 are the same or different and are independently selected from -(CH2) x’ -R 8 -R 9 , x' is 0, 1 or 2, R 8 is phenylene, R 9 -COOR 10 Or C≡N,R 10 H, C 1-4 alkyl; In the formula (II), R4 and R7 are the same or different and are independently selected from -(CH2) x’ -R 8 -R 9 , x' is 0, 1 or 2, R 8 is phenylene, R 9 C≡N; m is an integer from 3 to 40; R3, R5, R6 are the same or different and are independently selected from C 1-10 A straight chain or branched alkyl group; n is an integer from 1 to 20.

2. The co-assembly according to claim 1, characterized in that: The co-assembly is organic-organic co-assembly, which means that two organic substances are co-assembled using intermolecular interaction as a connecting force.

3. A fluorescence sensor array, characterized in that: The fluorescent sensor array is composed of more than one organic fluorescent sensor material arranged in sequence, and the organic fluorescent sensor material is obtained by co-assembling the carbazole derivatives represented by formula (I) and (II) in the co-assembly described in any one of claims 1 to 2.

4. The fluorescence sensor array according to claim 3, characterized in that: The organic fluorescent sensing material can perform fluorescence monitoring and differentiation on a variety of explosives.

5. The fluorescence sensor array according to claim 3, characterized in that: The fluorescent sensor array is composed of 1 to 8 kinds of organic fluorescent sensor materials arranged in sequence.

6. The fluorescence sensor array according to claim 3, characterized in that: The length of the organic fluorescent sensor material in the fluorescent sensor array is adjustable, and the distance between two adjacent materials is adjustable.

7. The fluorescence sensor array according to claim 6, characterized in that: In the fluorescent sensor array, the length of each organic fluorescent sensor material is 3 to 20 mm; and the distance between two adjacent organic fluorescent sensor materials is 5 to 50 mm.

8. The fluorescence sensor array according to claim 3, characterized in that: Each organic fluorescent sensing material in the fluorescent sensing array is an organic semiconductor nanowire or microbelt co-assembled from the carbazole derivatives described in formula (I) and (II).

9. The fluorescence sensor array according to claim 8, characterized in that: Each organic fluorescent sensing material in the fluorescent sensing array is a porous membrane with a mesh structure formed by self-assembly and weaving of the organic semiconductor nanowires or microbelts.

10. The method for preparing the co-assembly according to any one of claims 1 to 2, characterized in that: The method comprises the following steps: (1) synthesizing the carbazole derivatives represented by the formula (I) and (II), respectively; wherein each substituent is as defined above; (2) In a mixture of a good solvent and a poor solvent, the carbazole derivatives represented by formula (I) and (II) in step (1) are mixed and co-assembled to obtain the co-assembled product.

11. A method for preparing an organic fluorescent sensing material, characterized in that: The method comprises the method for preparing the co-assembly according to claim 10.

12. The method for preparing the fluorescent sensor array according to any one of claims 3 to 9, characterized in that: The method comprises the following steps: (1) synthesizing the carbazole derivatives represented by the formula (I) and (II), respectively; wherein each substituent is as defined above; (2) in a mixture of a good solvent and a poor solvent, the carbazole derivatives represented by formula (I) and (II) in step (1) are co-assembled to prepare at least one of the organic fluorescent sensing materials, (3) The organic fluorescent sensing material obtained in step (2) is applied to different positions inside the same glass tube to obtain the fluorescent sensing array.

13. The preparation method according to claim 12, characterized in that: In step (2), the molar ratio of the carbazole derivative represented by formula (I) to the carbazole derivative represented by formula (II) is 10 to 1000:

1.

14. Use of the fluorescent sensor array according to any one of claims 3 to 9, characterized in that: Used to distinguish explosives.

15. The use according to claim 14, characterized in that: The fluorescent sensor array performs rapid multiple continuous fluorescence detection and differentiation on explosives.

16. The use according to claim 15, characterized in that The fluorescent sensor array is used for rapid multiple continuous fluorescence detection and differentiation of solid explosives.

17. The use according to claim 16, characterized in that The explosive is selected from at least one of RDX, trinitrotoluene, pentaerythritol tetranitrate, ammonium nitrate, black powder and nitromethane.

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