CN107936946A - Fluorescence method distinguishes the preparation and application of the organic fluorescence sensor array of a few class explosives - Google Patents

Abstract

The present invention relates to a fluorescent sensing array composed of several fluorescent sensing materials that can detect and distinguish five types of explosives and its preparation method and application. The fluorescent sensing array is composed of several carbazole derivatives through π ‑π interaction self-assembled nanomaterials. The constituent materials in the fluorescent sensing array of the present invention are organic fluorescent sensing materials, which have typical characteristics of P-type materials and good luminescence stability, and the fluorescent sensing array composed of these materials has a good distinguishing effect on explosives.

Description

Fabrication and application of organic fluorescent sensor array for differentiating several types of explosives by fluorescence method

technical field

The invention belongs to a fluorescent sensing array composed of organic semiconductor fluorescent nanomaterials, in particular to the design, synthesis, assembly of sensing arrays of several P-type semiconductor materials based on carbazole molecules and the selective detection of the sensing array according to the difference in fluorescence response changes of the sensing array. Several classes of explosives are distinguished.

Background technique

Explosives pose a great threat to personal safety, national security, and the natural environment. Therefore, scientific researchers have done a lot of work in the detection and research of explosives. If explosives can be distinguished while detecting explosives, this is of great significance in anti-terrorism. Conventional explosives can be roughly divided into the following categories: nitroalkanes (DMNB), nitroaromatic compounds (DNT, TNT), nitroamines (RDX), nitroesters (PETN), black powder (S ), peroxides (TATP), etc. Currently, there are few methods for detecting and distinguishing explosives. Sensing arrays are widely used as a means of distinguishing. This method uses several types of materials to assemble sensing arrays, such as colorimetric sensing arrays, plus auxiliary analysis methods. It has been used to distinguish volatile organic compounds and toxic substances. Great progress has been made. Therefore, the sensor array can also be used as a means to distinguish explosives very well.

The fluorescent sensing array distinguishes explosives based on fluorescence detection of explosives. The main principle of the fluorescence method to detect and distinguish explosives is that several fluorescent molecular materials that make up the sensing array have different degrees of physical and chemical interactions with explosives to produce different fluorescence change signals, and then analyze the signals to achieve the purpose of differentiation. First, each type of explosive molecule has different chemical properties. For example, nitroaromatic explosives (DNT, TNT), such molecules have high vapor pressure and relatively good volatility; the nitro group on the aromatic ring has a strong electron-absorbing ability, which reduces the LUMO energy of the molecule, and the special nature of the aromatic ring Sex, this type of explosives has a strong binding force with fluorescent molecules, so this type of explosives is easy to detect, and there are many studies. However, nitroamine (RDX) and nitroester (PETN) explosives have low vapor pressure and poor volatility, and these molecules have poor electron donating ability, so they are relatively difficult to detect. However, S and peroxide explosive molecules are also difficult to detect because there is no chromophore. Therefore, it is particularly difficult to achieve the goal of distinguishing multiple types of explosives with a simple analysis using as few sensor arrays as possible.

At present, the array discrimination methods in the existing reports can distinguish fewer types of explosives, and most of them do not exceed three types. Moreover, these sensing arrays are complex in composition and expensive to manufacture, and cumbersome analysis methods are required in the process of differentiation. This obviously cannot meet the actual demand. It is challenging for researchers to implement simple sensing arrays to distinguish multiple types of explosives.

Contents of the invention

One of the objectives of the present invention is to provide a sensing array assembled from several organic fluorescent sensing materials that can perform high-sensitivity fluorescent detection and discrimination on several types of explosives.

The second object of the present invention is to provide a method for preparing several organic fluorescent sensing materials assembled into a sensing array capable of performing high-sensitivity fluorescent detection and discrimination on several types of explosives.

The third object of the present invention is to provide the application of a sensor array assembled from several types of organic fluorescent sensing materials that can distinguish several types of explosives with high sensitivity fluorescence detection.

The core purpose of the present invention is to prepare a fluorescent sensing array that can perform high-sensitivity fluorescent detection and discrimination on several types of explosives. The sensing array is composed of several different organic fluorescent sensing materials. Several materials combined into sensing arrays of the present invention are a series of P-type organic fluorescent sensing materials based on carbazole molecules, and each of these materials is obtained by changing the side chain of carbazole molecules and its polymerization The structure of carbazole derivatives with different side chains is synthesized, and several one-dimensional organic semiconductor nanowires or nanobelts are obtained through self-assembly methods. A sensing array assembled from several organic fluorescent sensing materials for high-sensitivity fluorescence detection and discrimination of substances. The materials combined into the sensing array in the present invention, that is, several kinds of nanowires or nanobelts assembled by molecules have larger specific surface areas and more surface pores, which are beneficial to the adsorption of the detected explosive vapor on the surface of the nanowires or nanobelts. Diffusion and better interaction, different fluorescent responses due to different surface physicochemical properties of the materials, several types of materials in the array respond uniquely to each type of explosive, so a fingerprint-like identification can be formed , so explosives can be differentiated. The organic fluorescent sensing materials obtained by the self-assembly of several side chain carbazole molecular derivatives with different substituent groups in the sensing array in the present invention have different shapes, namely nanobelts and nanowires, which are sensitive to different explosives. Different fluorescent responses, when used as a sensor array, can achieve differentiating effects according to different fluorescent responses. Therefore, the fluorescent sensing array of the present invention can be used as an organic fluorescent sensing array for detecting and distinguishing several types of explosives.

The present invention is achieved through the following technical solutions:

A fluorescent sensing array assembled from organic fluorescent sensing materials, wherein the fluorescent sensing array is composed of two or more organic fluorescent sensing materials that can monitor and distinguish several types of explosives in sequence, each The organic fluorescent materials are obtained by self-assembly of carbazole derivatives as described in formula (I) through π-π interaction:

In said formula (I),

R's are the same or different, independently selected from -(CH ₂ ) _x' -R ⁵ -R ⁶ , wherein, x' is 0, 1 or 2, R ⁵ is an arylene group or a halogenated arylene group, R ⁶ is H, -COOR ⁷ , -COR ⁷ , C _2-6 alkynyl, C≡N or C _3-6 alkyl, R ⁷ is H, C _1-4 alkyl;

n is an integer of 3-40;

R is selected from C _1-10 straight chain or branched chain alkyl, -(CH ₂ ) _x -R ¹ -OR ² , -(CH ₂ ) _y -R ¹ -R ³ or -(CH ₂ ) _z -R ⁴ ,

Wherein, x is 0, 1 or 2, y is 0, 1 or 2, z is an integer of 1-9, R ¹ is an arylene group or a halogenated arylene group, R ² is a C _1-10 straight chain or Branched chain alkyl, R ³ is -H, -CHF ₂ , -CF ₃ , C _1-10 straight chain or branched chain alkyl, C _3-10 cycloalkyl, C substituted by CHF ₂ or CF _{3 1-10} straight chain or branched chain alkyl, C _3-10 cycloalkyl, C _3-10 cycloalkyl substituted by CHF ₂ or CF ₃ , R ⁴ is -CHF ₂ , -CF ₃ .

Preferably, the fluorescent sensing array of the present invention is composed of 2 to 6 organic fluorescent sensing materials arranged in sequence.

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

According to the present invention, in the fluorescent sensing array, the length of each organic fluorescent sensing material is 3mm-20mm, adjustable, preferably 8-10mm; the distance between two adjacent materials is 5mm-50mm, adjustable, Preferably 15-20mm.

Further preferably, R's are the same or different, independently selected from -(CH ₂ ) _x' -R ⁵ -R ⁶ , x' is 0 or 1; R ⁵ is a haloarylene group (wherein the halogen is selected from fluorine , chlorine or bromine), such as halophenylene, arylene, such as phenylene or naphthylene; R ⁶ is C≡CH, C≡C-CH ₃ or C≡N;

Also preferably, R's are the same or different, independently selected from -(CH ₂ ) _x' -R ⁵ -R ⁶ , where x' is 0 or 1; R ⁶ is -COOR ⁷ , -COR ⁷ ; R ⁷ is methyl or ethyl;

Also preferably, R's are the same or different, and are independently selected from one of the following eight groups:

Wherein, the upper side is the connection site.

Preferably, R is selected from C _3-10 straight chain or branched chain alkyl, (CH ₂ ) _x -R ¹ -OR ² , -(CH ₂ ) _y -R ¹ -R ³ or -(CH ₂ ) _z -R ⁴ ,

Wherein, x is 0, 1 or 2, y is 0, 1 or 2, z is an integer of 2-6, R ¹ is phenylene or naphthylene or halogenated phenylene, R ² is C _1-10 straight chain or branched chain alkyl, R ³ is -H, -CF ₃ , C _1-10 straight chain or branched chain alkyl or CF ₃ substituted C _1-10 straight chain or branched chain alkyl, R ⁴ is -CF ₃ .

Preferably, R is selected from C _3-10 branched chain alkyl groups, and the branched chain alkyl groups are asymmetric alkyl groups.

Also preferably, R is selected from one of the following groups:

In the above groups, the upper side of the structural formula is the linking point.

According to the fluorescent sensing array of the present invention, each material in the described organic fluorescent sensing material is obtained by self-assembly of a carbazole derivative as described in formula (I) through π-π interaction organic semiconductor nanowires or nanobelts.

Further, each of the organic fluorescent sensing materials is a porous film with a network structure formed by self-assembly and weaving of the organic semiconductor nanowires or nanobelts.

The present invention also provides a method for preparing a fluorescent sensor array, characterized in that the method comprises the following steps:

(1) Synthesizing the carbazole derivatives shown in the formula (I) with special functional groups,

Wherein each substituent is as defined above;

(2) in the mixed solution of good solvent and poor solvent, obtain described several kinds of organic fluorescent sensing materials by the mode of self-assembly,

(3) Apply the assembled fluorescent materials to different positions inside the same glass tube to obtain the sensing array.

According to the present invention, in step (1):

When preparing the carbazole derivatives of n=3 in the formula (I), the step (1) specifically includes:

(1a) the compound shown in the formula (II) reacts with RX ' to prepare the compound shown in the formula (III);

X in formula (II) 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); Formula (III) and The definition of R in RX' is the same as formula (I);

(1b) Compound shown in _formula (III) reacts with R'B(OH) to prepare compound shown in formula (IV);

In formula (IV) and R'B(OH) ₂ , the definition of R' is the same as formula (I); In formula (IV), the definition of R and X is the same as formula (III);

(1c) reacting the compound shown in formula (III) with dipivaloyl diboron to prepare the compound shown in formula (V);

In formula (V), the definition of R is the same as formula (I);

(1d) react the compound shown in the formula (IV) with the compound shown in the formula (V) to obtain the carbazole derivative shown in the formula (I), wherein n=3; Wherein, the compound shown in the formula (IV) and the compound shown in the formula (V) The molar ratio of the compounds shown is 2.1:1 to 2.5:1 (for example, 2.2:1);

When preparing the carbazole derivatives of 3<n≤40 in the formula (I), the step (1) specifically includes:

(1a) the compound shown in the formula (II) reacts with RX ' to prepare the compound shown in the formula (III);

X in formula (II) 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); Formula (III) and The definition of R in RX' is the same as formula (I);

(1a') the compound shown in the formula (II') reacts with RX' to prepare the compound shown in the formula (III');

X in formula (II') 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); Formula (III The definition of R in ') and RX' is the same as formula (I); m is an integer of 2-38;

(1b) Compound shown in _formula (III) reacts with R'B(OH) to prepare compound shown in formula (IV);

In formula (IV) and R'B(OH) ₂ , the definition of R' is the same as formula (I); In formula (IV), the definition of R and X is the same as formula (III);

(1c') Compound shown in formula (III') reacts with bis-valeryl diboron to prepare compound shown in formula (V');

In formula (V'), the definition of R is the same as formula (I), and m is an integer of 2-38;

(1d') The compound shown in the formula (IV) reacts with the compound shown in the formula (V') to obtain the carbazole derivative shown in the formula (I), wherein 3<n≤40; Wherein, the compound shown in the formula (IV) and The molar ratio of the compound represented by the formula (V') is 2.1:1 to 2.5:1 (for example, 2.2:1).

Preferably, the step (2) includes: dissolving the carbazole derivatives shown in the formula (I) obtained in the step (1) with different special functional groups in a good solvent, then adding a poor solvent, standing still, the formula (1) the suspension of the carbazole derivative shown in the self-assembly mode of the organic fluorescent sensing material;

Preferably, the step (2) further includes: after the suspension of the several organic fluorescent sensing materials is left to stand, take out the organic fluorescent sensing material located at the bottom of the preparation container, place it again in a poor solvent and shake to disperse evenly and repeatedly washing to obtain the organic fluorescent sensing material;

Preferably, the volume ratio (ml:ml) of the good solvent to the poor solvent is 1:3 to 1:10;

Preferably, the good solvent is selected from chlorinated alkanes and _C2-5 esters, such as dichloromethane, chloroform, 1,2-dichloroethane, ethyl acetate or methyl acetate;

Preferably, the poor solvent is an alcoholic organic solvent or a cycloalkane, such as methanol, ethanol or cyclohexane.

Preferably, the step (3) includes: sequentially injecting the suspension of the organic fluorescent sensing material obtained in the step (2) into the same glass tube, waiting for the solvent to evaporate, and remembering the organic fluorescent sensing array.

The fluorescent sensing array of the present invention is composed of porous film materials with a network structure formed by several organic semiconductor nanowires or nanobelts. These materials have high specific surface areas and have different fluorescent responses to different explosives. According to the fluorescent response After analysis, several types of explosives can be detected and distinguished.

The present invention also provides the application of the fluorescent sensing array in distinguishing several types of explosives, wherein the fluorescent sensing array is composed of several organic fluorescent sensing materials.

According to the present invention, the fluorescent sensing array can perform rapid fluorescent detection and distinction on several types of explosives.

According to the present invention, the fluorescent sensing array can be used for detecting and distinguishing solid explosives.

According to the application of the present invention, the fluorescent sensing array can be used to detect and distinguish trace amounts of several types of explosives, and the trace amounts are ng or sub-ng levels.

In the present invention, when the fluorescent sensing array is in contact with trace explosives (the explosives are preferably solid) vapor, because each fluorescent material has different substituted functional group side chains and different shapes, it has different The physical and chemical properties of the surface will cause different forms of fluorescence changes. By analyzing the signals of these fluorescence changes, it can be used to detect and distinguish several types of explosives.

The obtained different sensing materials are spin-coated in the quartz glass tube, and the vapor concentration of the explosive is increased by placing the explosive in the heat gun and setting different temperatures. When the organic fluorescent sensing materials are in contact with each other, the fluorescence of the different fluorescent sensing materials will change in different forms, and the purpose of detecting and distinguishing several types of explosives can be achieved by analyzing the fluorescence change signals.

Described several classes of explosives are selected from RDX, trinitrotoluene (TNT), dinitrotoluene (DNT), pentaerythritol tetranitrate (PETN), ammonium nitrate (AN), black powder (S) , nitromethane (NM) and 2,3-dinitro-2,3-dimethylbutane (DMNB).

The main constituent material of the fluorescent sensing array of the present invention is a typical P-type semiconductor fluorescent sensing material. The present invention designs and modifies the substituting functional groups and the degree of polymerization of the main body. When the several designed organic fluorescent sensing materials formed in this way interact with the high-temperature steam of explosives containing nitro groups, different degrees of electron transfer or strength will occur. Different physical adsorption causes different forms of fluorescence changes in several organic fluorescent sensing 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 array of fluorescence changes thus obtained in different forms is different and specific to each class of explosive. Therefore, this sensing array composed of several different organic fluorescent sensing materials can quickly detect and distinguish several types of explosives.

It should be noted that the several types of explosives mentioned in the present invention are distinguished according to the types, and one type of explosives may contain one or more types of explosives.

Beneficial effects of the present invention:

The organic fluorescent sensing material used in the present invention is self-assembled by carbazole derivatives through π-π interaction, and can form different forms of fluorescence changes for different explosives by modifying the specific substitution functional group side chain and polymerization degree on the main body , the present invention forms a sensor array by assembling several such organic fluorescent sensing materials with different fluorescence changes, forms a unique fluorescence change array for each explosive, and realizes fluorescent discrimination of several types of explosives .

The sensing array of the invention can detect and distinguish several types of explosives at the ng level, has high detection and distinguishing sensitivity, and the composition and operation of the sensing array are more convenient. After design, this sensing array can be further made into a portable device that can quickly detect and distinguish several types of explosives, and apply and serve the society. This is a work of great significance and has far-reaching application and development prospects. .

The invention also provides a simple and efficient preparation method for several organic fluorescent sensing materials in the sensing array. The synthesis route of the method is simple, which is convenient for large-scale preparation, and the nanowire growth method is simple and fast.

Description of drawings

Fig. 1. Schematic diagram of the structure of the fluorescent sensing array of the present invention.

Fig. 2. The NMR data spectrum of the carbazole derivative in which R is n-octane and n is 3 in Example 1 of the present invention.

Fig. 3. The mass spectrometry data diagram of the carbazole derivative in which R is n-octane and n is 3 in Example 1 of the present invention.

Fig. 4. NMR data spectrum of the carbazole derivative in which R is benzyl and n is 3 in Example 2 of the present invention.

Fig. 5. SEM image of organic semiconductor nanowires with ultra-sensitive fluorescence response constructed by carbazole derivatives with R being n-octane and n being 3 in Example 1 of the present invention.

Figure 6. In Example 1 of the present invention, R is n-octane, and n is a carbazole derivative of 3, which has ultra-sensitive fluorescence response. The organic semiconductor nanowire self-assembled and woven mesh structure porous membrane and this Invention Example 2, where R is isobutyl and n is 3 carbazole derivatives, the sensing array pair is composed of a network structure porous membrane formed by organic semiconductor nanowires self-assembled and woven with ultra-sensitive fluorescence response Detection fluorescence curve of TNT. 1.1<Q2/Q1<2.

Figure 7. In Example 1 of the present invention, R is n-octane, and n is 3 carbazole derivatives. The organic semiconductor nanowires self-assembled and woven with ultra-sensitive fluorescence response. The porous membrane and the present invention Invention Example 2, where R is isobutyl and n is 3 carbazole derivatives, the sensing array pair is composed of a network structure porous membrane formed by organic semiconductor nanowires self-assembled and woven with ultra-sensitive fluorescence response DNT detection fluorescence curve. 1.1<Q2/Q1<2.

Figure 8. In Example 1 of the present invention, R is n-octane, and n is 3 carbazole derivatives. The organic semiconductor nanowires self-assembled and woven with ultra-sensitive fluorescent response. The porous membrane and the present invention Invention Example 2, where R is isobutyl and n is 3 carbazole derivatives, the sensing array pair is composed of a network structure porous membrane formed by organic semiconductor nanowires self-assembled and woven with ultra-sensitive fluorescence response Detection fluorescence curve of S. 2.1<Q2/Q1<4.5.

Figure 9. In Example 1 of the present invention, R is n-octane, and n is 3 carbazole derivatives, which have supersensitive fluorescence response, organic semiconductor nanowires self-assembled and woven to form a network-like porous membrane and the present invention. Invention Example 2, where R is isobutyl and n is 3 carbazole derivatives, the sensing array pair is composed of a network structure porous membrane formed by organic semiconductor nanowires self-assembled and woven with ultra-sensitive fluorescence response Detection fluorescence curve of RDX. 2.1<Q1/Q2<4.0.

Figure 10. In Example 1 of the present invention, R is n-octane, and n is 3 carbazole derivatives. The organic semiconductor nanowires self-assembled and woven with ultra-sensitive fluorescence response. The porous membrane and the present invention Invention Example 2, where R is isobutyl and n is 3 carbazole derivatives, the sensing array pair is composed of a network structure porous membrane formed by organic semiconductor nanowires self-assembled and woven with ultra-sensitive fluorescence response Detection fluorescence curve of PETN. 2.1<Q1/Q2<4.0.

Figure 11. In Example 1 of the present invention, where R is n-octane and n is 3 carbazole derivatives, the organic semiconductor nanowires self-assembled and woven with ultra-sensitive fluorescence response is constructed to form a network-like porous membrane and the present invention. Invention Example 2, where R is isobutyl and n is 3 carbazole derivatives, the sensing array pair is composed of a network structure porous membrane formed by organic semiconductor nanowires self-assembled and woven with ultra-sensitive fluorescence response Detection fluorescence curve of DMNB. The fluorescence response was recovered by nearly 100%.

Figure 12. In Example 1 of the present invention, where R is n-octane and n is 3 carbazole derivatives, the organic semiconductor nanowire self-assembled and woven network structure porous membrane with ultrasensitive fluorescence response and the present invention Invention Example 2, where R is isobutyl and n is 3 carbazole derivatives, the sensing array pair is composed of a network structure porous membrane formed by organic semiconductor nanowires self-assembled and woven with ultra-sensitive fluorescence response AN detection fluorescence curve. 1.1<Q1/Q2<2.0.

Figure 13. In Example 1 of the present invention, where R is n-octane and n is 3 carbazole derivatives, the organic semiconductor nanowires self-assembled and woven with ultra-sensitive fluorescence response constitutes a porous membrane with a network structure. The fluorescent response of explosives is named as Q1. In Example 2 of the present invention, R is isobutyl, and n is a carbazole derivative of 3. It is a network formed by self-assembly and weaving of organic semiconductor nanowires with ultra-sensitive fluorescent response. The fluorescent response of the sensor array composed of a porous membrane with a structure like structure to four types of explosives is named Q2, according to the diagrams drawn by Q1/Q2 and Q2/Q1.

Figure 14. In Example 1 of the present invention, where R is n-octane and n is 3 carbazole derivatives, the organic semiconductor nanowire self-assembled and woven network structure porous membrane with ultrasensitive fluorescence response and the present invention Invention Example 2, where R is isobutyl and n is 3 carbazole derivatives, the sensing array pair is composed of a network structure porous membrane formed by organic semiconductor nanowires self-assembled and woven with ultra-sensitive fluorescence response Detection fluorescence curve of NM. The fluorescence response was recovered by nearly 100%.

Detailed ways

As mentioned above, the present invention discloses a method for preparing an organic fluorescent sensing material that can be distinguished by high-sensitivity fluorescence detection for several types of explosives. In a preferred embodiment of the present invention, n=3 in the preparation formula (I) The carbazole derivative, the step (1) specifically includes:

(1a) the compound shown in the formula (II) reacts with RX ' to prepare the compound shown in the formula (III);

X in formula (II) 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); Formula (III) and The definition of R in RX' is the same as formula (I);

(1b) Compound shown in _formula (III) reacts with R'B(OH) to prepare compound shown in formula (IV);

In formula (IV) and R'B(OH) ₂ , the definition of R' is the same as formula (I); In formula (IV), the definition of R and X is the same as formula (III);

(1c) reacting the compound shown in formula (III) with dipivaloyl diboron to prepare the compound shown in formula (V);

In formula (V), the definition of R is the same as formula (I);

(1d) react the compound shown in the formula (IV) with the compound shown in the formula (V) to obtain the carbazole derivative shown in the formula (I), wherein n=3; Wherein, the compound shown in the formula (IV) and the compound shown in the formula (V) The molar ratio of the compounds shown is 2.1:1 to 2.5:1 (eg 2.2:1).

In another preferred embodiment of the present invention, the carbazole derivatives of 3<n≤40 in the preparation formula (I), the step (1) specifically includes:

(1a) the compound shown in the formula (II) reacts with RX ' to prepare the compound shown in the formula (III);

X in formula (II) 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); Formula (III) and The definition of R in RX' is the same as formula (I);

(1a') the compound shown in the formula (II') reacts with RX' to prepare the compound shown in the formula (III');

X in formula (II') 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); Formula (III The definition of R in ') and RX' is the same as formula (I); m is an integer of 2-38;

(1b) Compound shown in _formula (III) reacts with R'B(OH) to prepare compound shown in formula (IV);

In formula (IV) and R'B(OH) ₂ , the definition of R' is the same as formula (I); In formula (IV), the definition of R and X is the same as formula (III);

(1c') Compound shown in formula (III') reacts with bis-valeryl diboron to prepare compound shown in formula (V');

In formula (V'), the definition of R is the same as formula (I), and m is an integer of 2-38;

(1d') The compound shown in the formula (IV) reacts with the compound shown in the formula (V') to obtain the carbazole derivative shown in the formula (I), wherein 3<n≤40; Wherein, the compound shown in the formula (IV) and The molar ratio of the compound represented by the formula (V') is 2.1:1 to 2.5:1 (for example, 2.2:1).

In the above step (1a) or (1a'), the reaction is carried out in a solvent. The solvent is an organic solvent that can dissolve the compound shown in formula (II) or formula (II'), such as an amide compound, specifically selected from N,N-dimethyl-formamide.

In the above step (1a) or (1a'), the reaction is carried out at a temperature of -10 to 10°C, preferably -5 to 5°C.

In the above step (1a), the reaction is carried out under the action of a catalyst. The catalyst is, for example, sodium hydride. The equivalent ratio of the compound represented by formula (II) to the catalyst is 1:1.1˜1:1.3, preferably 1:1.2.

In above-mentioned step (1a'), described reaction is carried out under the effect of catalyst. The catalyst is, for example, sodium hydride. The equivalent ratio of the compound shown in formula (II') to the catalyst is 1:(m+0.1)～1:(m+0.3), preferably 1:(m+0.2), and m is an integer of 2-38.

In the above step (1a), the equivalent ratio of the compound of formula (II) to RX' is 1.1.2 to 1:1.5, preferably 1:1.3.

In the above step (1a'), the equivalent ratio of the compound of formula (II') to RX' is 1:(m+0.2)～1:(m+0.5), preferably 1:(m+0.3), m is 2 Integer of -38.

In a preferred technical scheme, the carbazole derivatives with n=3 in the formula (I) are prepared, and the step (1a) is specifically: dissolving 1 equivalent of 2,7-dibromocarbazole in N,N- Dimethyl-formamide is configured into a solution with a concentration of 1g/30ml. The above solution is placed in an ice bath at 0°C, and 1.2 equivalents of sodium hydride solid is slowly added. After stirring for half an hour, 1.5 equivalents of 1- Bromooctane, 2-bromobutane, 4-trifluoromethylbenzyl bromide, benzyl bromide or 4-methoxybenzyl bromide, after reacting overnight at room temperature, the product was obtained by column chromatography.

In the above step (1b), the reaction is carried out in a solvent. The solvent is an organic solvent capable of dissolving the compound represented by formula (III), such as an epoxy compound, specifically 1,4-dioxane.

In the above step (1b), the equivalent ratio of the compound of formula (III) to R'B(OH) ₂ is 1:1.

In the above step (1b), the reaction is carried out in a catalyst system comprising tetrakis(triphenylphosphine)palladium and cesium carbonate. With respect to 1 equivalent of the compound of formula (III), the added amount of tetrakis(triphenylphosphine) palladium is 5-15% equivalent, and the added amount of cesium carbonate is 2.5-3.5 equivalent.

In the above step (1b), the reaction is carried out under the protection of an inert gas, the reaction temperature is 70-90° C., and the reaction time is 6-8 hours.

In a preferred embodiment, the step (1b) is specifically: (1b) take 1 equivalent of the product obtained in the step (1a), dissolve it in 1,4-dioxane and configure it to a concentration of 1g/20ml solution, add 1 equivalent of p-methoxycarbonylphenylboronic acid, 10% equivalent of tetrakis (triphenylphosphine) palladium, and 3 equivalents of cesium carbonate at 80°C under the protection of argon, react for 6 hours, and obtain by column chromatography product.

In the above step (1c) or (1c'), the reaction is carried out in a solvent. The solvent is an organic solvent that can dissolve the compound represented by formula (III) or formula (III'), such as an epoxy compound, specifically 1,4-dioxane.

In the above step (1c) or (1c'), the equivalent ratio of the compound of formula (III) or formula (III') to bis-valeryl diboron is 1:4-6.

In the above step (1c) or (1c'), the reaction is carried out in a catalyst system comprising potassium acetate and [1,1'-bis(diphenylphosphino)ferrocene] dichloride palladium. With respect to the compound of formula (III) formula (III') of 1 equivalent, the addition amount of potassium acetate is 10～20 equivalents, [1,1'-bis (diphenylphosphino) ferrocene] palladium dichloride The addition amount is 5-15% equivalent.

In the above step (1c) or (1c'), the reaction is carried out under the protection of an inert gas, the reaction temperature is 70-80°C, and the reaction time is 4-8 hours.

In a preferred embodiment, the carbazole derivatives with n=3 in the formula (I) are prepared, and the step (1c) is specifically: taking 1 equivalent of the product obtained in the step (1a), adding 1,4-di Oxycycline is configured into a solution with a concentration of 1g/20ml, and 5 equivalents of bis-valeryl diboron, 14 equivalents of potassium acetate, and 10% equivalents of [1,1'-bis(diphenylphosphino)dicene Iron]palladium dichloride was reacted for 6 hours under argon protection at 80°C, and the product was obtained by column chromatography.

In the above step (1d) or (1d'), the reaction is carried out in a solvent. The solvent is an organic solvent that can dissolve the compounds shown in formula (VI), formula (V) and formula (V'), such as aromatic hydrocarbons, specifically benzene or toluene.

In the above step (1d) or (1d'), the equivalent ratio of the compound of formula (VI) to the compound of formula (V) or formula (V') is 1:2.2.

In the above step (1d) or (1d'), the reaction is carried out in a catalyst system, and the catalyst system includes tetrakis (triphenylphosphine) palladium and potassium carbonate. With respect to 1 equivalent of the compound of formula (III), the added amount of potassium carbonate is 3-5 equivalents, and the added amount of tetrakis(triphenylphosphine)palladium is 5-15% equivalents.

In the above step (1d) or (1d'), the reaction is carried out under the protection of an inert gas, the reaction temperature is 70-90°C, and the reaction time is 12-48 hours.

In a preferred embodiment, to prepare carbazole derivatives with n=3 in formula (I), the step (1d) is specifically: take 1 mmol and 2.2 mmol of the products obtained in step (1c) and step (1b) respectively , was added to 20ml of toluene solution, 10% tetrakis(triphenylphosphine) palladium and 3 equivalents of potassium carbonate were added, under the protection of argon at 80°C, after overnight reaction, the product was obtained by column chromatography.

In order to further illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be described in detail below in conjunction with specific embodiments and with reference to the accompanying drawings. However, those skilled in the art understand that the present invention is not limited to the drawings and the following embodiments.

Example 1

Preparation has the following molecular 1 R is a straight-chain octyl group, R' is a 4-methoxycarbonylphenyl group, and n is a carbazole derivative of 3, and its preparation method is as follows:

(1) Dissolve 1 g of 2,7-dibromocarbazole in 30 ml of N,N-dimethyl-formamide (DMF) solution, place the above solution in an ice bath at 0°C, and slowly add 1.2 The equivalent of 74 mg of sodium hydride solid was continuously stirred for half an hour, then 1.5 equivalent of 1-bromooctane was slowly added, and after reacting overnight at room temperature, the product was obtained by column chromatography.

(2) Get 500 mg of the product obtained in step (1), add 20 ml of 1,4-dioxane solution, add 5 equivalents of bisvaleryl diboron, 14 equivalents of potassium acetate, 10% equivalents of [1,1 '-bis(diphenylphosphino)ferrocene]palladium dichloride was reacted for 6 hours at 80°C under the protection of argon, and the product (TM-1) was obtained by column chromatography.

(3) Take 500 mg of the product obtained in step (1), add 20 ml of 1,4-dioxane solution, add 1 equivalent of p-methylcarbonylphenylboronic acid, 10% equivalent of tetrakis (triphenylphosphine) palladium, 3 equivalents of cesium carbonate were reacted under the protection of argon at 80°C for 6 hours, and the product was obtained by column chromatography.

(4) get the product 1mmol and 2.2mmol that step (2) and step (3) obtain respectively, join in the 20ml toluene solution, add 10% tetrakis (triphenylphosphine) palladium, 3 equivalents of salt of wormwood at 80 ℃ Under the protection of argon, after reacting overnight, the product (molecule 1) was obtained by column chromatography; its nuclear magnetic resonance data diagram is shown in Figure 2;

(5) The carbazole derivative (molecule 2) with p-methylcarbonylphenyl that n obtained in step (4) is 3 is dissolved in a good solvent and then added to a poor solvent, and the good solvent is ethyl acetate, One of dichloromethane, chloroform or 1,2-dichloroethane, the poor solvent is one of methanol, ethanol or cyclohexane, the volume ratio of good solvent to poor solvent is 1:3～1 : 10; standing still, the carbazole derivatives with p-methylcarbonylbenzene obtain the suspension of organic semiconductor nanowires or nanobelts with different fluorescent responses to several types of explosives by self-assembly.

Example 2

Preparation has the following molecular 2 R is a benzyl group, R' is a 4-methoxycarbonylphenyl group, and n is a carbazole derivative of 3, and its preparation method is as follows:

(1) Dissolve 1 gram of 2,7-dibromocarbazole in 30 milliliters of N,N-dimethyl-formamide (DMF) solution, place the above solution in an ice bath at 0°C, and slowly add 1.2 Equivalent of 74 mg of sodium hydride solid, after continuous stirring for half an hour, 1.5 equivalent of benzyl bromide was slowly added, and after reacting overnight at room temperature, the product was obtained by column chromatography.

(2) Get 500 mg of the product obtained in step (1), add 20 ml of 1,4-dioxane solution, add 5 equivalents of bisvaleryl diboron, 14 equivalents of potassium acetate, 10% equivalents of [1,1 '-bis(diphenylphosphino)ferrocene]palladium dichloride was reacted for 6 hours at 80°C under the protection of argon, and the product (TM-1) was obtained by column chromatography.

(3) Take 500 mg of the product obtained in step (1), add 20 ml of 1,4-dioxane solution, add 1 equivalent of p-methoxycarbonylphenylboronic acid, 10% equivalent of tetrakis (triphenylphosphine) palladium , 3 equivalents of cesium carbonate were reacted for 6 hours at 80°C under the protection of argon, and the product was obtained by column chromatography.

(4) get the product 1mmol and 2.2mmol that step (2) and step (3) obtain respectively, join in the 20ml toluene solution, add 10% tetrakis (triphenylphosphine) palladium, 3 equivalents of salt of wormwood at 80 ℃ Under the protection of argon, after reacting overnight, the product (molecule 2) was obtained by column chromatography; the mass spectrum data MALDI-TOF (m/z) = 1035.4; the NMR data diagram is shown in FIG. 4 .

(5) Dissolving the carbazole derivative with n being 3 obtained in step (4) in a good solvent and then adding the poor solvent, the good solvent is one of dichloromethane, chloroform or 1,2-dichloroethane A kind of, described poor solvent is a kind of in methanol, ethanol or cyclohexane, and the volume ratio of good solvent and poor solvent is 1:2～1:15; Stand still, described carbazole derivative obtains by self-assembly mode Suspensions of organic semiconductor nanowires with fluorescent responses to several classes of explosives.

Example 3

Take the suspension prepared by the carbazole derivative with 4-cyanophenyl in step (5) of Example 1 and take out the sample at the bottom of the container with a pipette gun and place it on a clean silicon wafer surface. After the volatilization, it was placed in an ion sputtering machine (Leica), and the vacuum was evacuated to 10 ^-4 Pa, and then metal platinum particles were sputtered on the surface for 120 s. The silicon wafer was taken out and placed in a scanning electron microscope (Hitachi S8010) to observe its morphology. As can be seen in a, b and c in Figure 5, the one-dimensional organic semiconductor nanoribbons self-assemble and weave to form a unique network-like porous structure, which provides a special fluorescent response signal for detection and discrimination.

Example 4

After the suspension obtained in Step (5) of Example 1 and Step (5) of Example 2 was left to stand for 24 hours, the film at the bottom of the container was taken out and applied to different positions in the same quartz glass tube successively to prepare two kinds of materials fluorescent sensor array. The porous membrane coated in the quartz glass tube was excited using a 380 nm excitation light source. Using a solid explosive detector, use a pipette gun to pipette 0.3ng, 0.5ng, and 0.8ng TNT drops into the heating gun, set the heating temperature to 170°C, and blow TNT vapors of different concentrations on the surface of the porous membrane , the detection results showed the fluorescence changes as shown in Figure 6 at the three concentrations.

Example 5

Using the same method as in Example 4, except that the detection substance was replaced by 0.3ng, 0.5ng, and 0.8ng DNT, the detection results showed fluorescence changes as shown in Figure 7 at the three concentrations.

Example 6

Using the same method as in Example 4, except that the detection substance was replaced by 0.2ng, 0.5ng, and 1ng S, the detection results showed fluorescence changes as shown in Figure 8 at the three concentrations.

Example 7

Using the same method as in Example 4, the detected substance was replaced with 0.1ng, 0.2ng, and 0.5ng RDX, and the detection results showed fluorescence changes as shown in Figure 9 at the three concentrations.

Example 8

Using the same method as in Example 4, the detected substance was replaced with 0.5ng, 1ng, and 2ng PETN, and the detection results showed fluorescence changes as shown in Figure 10 at the three concentrations.

Example 9

Using the same method as in Example 4, the detected substance was replaced with 30ng, 50ng, and 80ng DMNB, and the detection results showed fluorescence changes as shown in Figure 11 at the three concentrations.

Example 10

Using the same method as in Example 4, the detected substance was replaced with 10ng, 20ng, and 30ng AN, and the detection results showed fluorescence changes as shown in Figure 12 at the three concentrations.

The sensing array composed of two organic fluorescent derivatives (material 1 and material 2) obtained by self-assembly of carbazole derivatives with different functional group side chains in embodiment 1 and embodiment 2 is effective for the above eight explosives Pattern analysis of the fluorescence response changes. Name the fluorescent response of material 1 as Q1, and the fluorescent response of material 2 as Q2. According to the ratio analysis of Q1/Q2 and Q2/Q1, the change of the fluorescent response of the sensor array to each type of explosive is unique, as shown in Figure 13 . Through analysis, it is found that the fluorescence response of the two materials to DMNB and NM will recover nearly 100% after fluorescence quenching (as shown in Figure 14), while the two materials will not recover to other explosives, so the five types of Classification of explosives. Therefore, it can be determined which type of explosive the detected explosive is based on the response of the sensing array composed of the two materials.

Example 11

(1) Dissolve 1 g of 2,7-dibromocarbazole in 30 ml of N,N-dimethyl-formamide (DMF) solution, place the above solution in an ice bath at 0°C, and slowly add 1.2 The equivalent of 74 mg of sodium hydride solid was continuously stirred for half an hour, then 1.5 equivalent of 1-bromooctane was slowly added, and after reacting overnight at room temperature, the product was obtained by column chromatography.

(2) Get 500 mg of the product obtained in step (1), add 20 ml of 1,4-dioxane solution, add 5 equivalents of bisvaleryl diboron, 14 equivalents of potassium acetate, 10% equivalents of [1,1 '-bis(diphenylphosphino)ferrocene]palladium dichloride was reacted for 6 hours at 80°C under the protection of argon, and the product (TM-1) was obtained by column chromatography.

(3) Take 500 mg of the product obtained in step (1), add 20 ml of 1,4-dioxane solution, add 1 equivalent of p-cyanophenylboronic acid, 10% equivalent of tetrakis (triphenylphosphine) palladium, 3 An equivalent amount of cesium carbonate was reacted under the protection of argon at 80° C. for 6 hours, and the product (TM-2) was obtained by column chromatography.

(4) get the product 1mmol and 2.2mmol that step (2) and step (3) obtain respectively, join in the 20ml toluene solution, add 10% tetrakis (triphenylphosphine) palladium, 3 equivalents of salt of wormwood at 80 ℃ Under the protection of argon, after reacting overnight, the carbazole derivative in formula (I) in which R is a linear octyl group, R' is 4-cyanophenyl, and n is 4 is obtained by column chromatography.

(5) The carbazole derivative with 4-cyanophenyl that n is 4 that step (4) obtains is dissolved in good solvent and then add poor solvent, and described good solvent is ethyl acetate, dichloromethane, One of chloroform or 1,2-dichloroethane, the poor solvent is one of methanol, ethanol or cyclohexane, the volume ratio of good solvent to poor solvent is 1:3～1:10; The carbazole derivatives with 4-cyanophenyl can be self-assembled to obtain suspensions of organic semiconductor nanowires or nanobelts with different fluorescence responses to several types of explosives.

Example 12

(1) Dissolve 1 g of 2,7-dibromocarbazole in 30 ml of N,N-dimethyl-formamide (DMF) solution, place the above solution in an ice bath at 0°C, and slowly add 1.2 The equivalent of 74 mg of sodium hydride solid was continuously stirred for half an hour, then 1.5 equivalent of 1-bromooctane was slowly added, and after reacting overnight at room temperature, the product was obtained by column chromatography.

(2) Get 500 mg of the product obtained in step (1), add 20 ml of 1,4-dioxane solution, add 5 equivalents of bisvaleryl diboron, 14 equivalents of potassium acetate, 10% equivalents of [1,1 '-bis(diphenylphosphino)ferrocene]palladium dichloride was reacted for 6 hours at 80°C under the protection of argon, and the product (TM-1) was obtained by column chromatography.

(3) Take 500 mg of the product obtained in step (1), add 20 ml of 1,4-dioxane solution, add 1 equivalent of p-methylcarbonylphenylboronic acid, 10% equivalent of tetrakis (triphenylphosphine) palladium, 3 equivalents of cesium carbonate were reacted for 6 hours under the protection of argon at 80°C, and the product (TM-2) was obtained by column chromatography.

(4) get the product 1mmol and 2.2mmol that step (2) and step (3) obtain respectively, join in the 20ml toluene solution, add 10% tetrakis (triphenylphosphine) palladium, 3 equivalents of salt of wormwood at 80 ℃ Under the protection of argon, after reacting overnight, the carbazole derivative in formula (I) in which R is a linear octyl group, R' is p-methylcarbonylphenyl, and n is 4 is obtained by column chromatography.

(5) The carbazole derivative with p-methylcarbonylphenyl that n is 4 obtained in step (4) is dissolved in a good solvent and then added to a poor solvent, and the good solvent is ethyl acetate, dichloromethane, One of chloroform or 1,2-dichloroethane, the poor solvent is one of methanol, ethanol or cyclohexane, the volume ratio of good solvent to poor solvent is 1:3～1:10; The carbazole derivatives with 4-methylcarbonylphenyl are self-assembled to obtain suspensions of organic semiconductor nanowires or nanobelts with different fluorescence responses to several types of explosives.

It has been determined that the sensing array composed of the above two sensing materials with n being 4 has similar response changes to several types of explosives as the sensing array composed of sensing materials in Example 1 and Implementation 2, and can also be It plays the role of fluorescence detection and distinction for several types of explosives.

The embodiments of the present invention have been described above. However, the present invention is not limited to the above-mentioned embodiments. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims (10)

1. A fluorescent sensing array, characterized in that: the fluorescent sensing array is composed of two or more organic fluorescent sensing materials that can carry out fluorescence monitoring and distinction to several types of explosives, and each of the organic fluorescent sensing materials Fluorescent materials are all self-assembled by a carbazole derivative as described in formula (I) through π-π interaction: In the formula (I), R' is the same or different, independently selected from -(CH ₂ ) _x' -R ⁵ -R ⁶ , wherein, x' is 0, 1 or 2, and R ⁵ is an arylene group Or halogenated arylene, R ⁶ is H, -COOR ⁷ , -COR ⁷ , C _2-6 alkynyl, C≡N or C _3-6 alkyl, R ⁷ is H, C _1-4 alkyl ; n is an integer of 3-40; R is selected from C _1-10 straight or branched chain alkyl, -(CH ₂ ) _x -R ¹ -OR ² , -(CH ₂ ) _y -R ¹ -R ³ Or -(CH ₂ ) _z -R ⁴ , wherein, x is 0, 1 or 2, y is 0, 1 or 2, z is an integer of 1-9, R ¹ is an arylene group or a haloarylene group, R ² is C _1-10 straight chain or branched chain alkyl, R ³ is -H, -CHF ₂ , -CF ₃ , C _1-10 straight chain or branched chain alkyl, substituted by CHF ₂ or CF ₃ C _1-10 straight chain or branched chain alkyl, C _3-10 cycloalkyl, C _3-10 cycloalkyl substituted by CHF ₂ or CF ₃ , R ⁴ is -CHF ₂ , -CF ₃ . 2. The fluorescent sensing array according to claim 1, characterized in that: the fluorescent sensing array is composed of 2 to 6 kinds of the organic fluorescent sensing materials arranged in sequence. Preferably, in the fluorescent sensing array, the length of each organic fluorescent sensing material is 3mm-20mm, adjustable, preferably 8-10mm; the distance between two adjacent materials is 5mm-50mm, adjustable, preferably 15-20mm. 3. The fluorescent sensor array according to claim 1 or 2, characterized in that: the R's are the same or different, independently selected from -(CH ₂ ) _x' -R ⁵ -R ⁶ , where x ' is 0 or 1, R ⁵ is an arylene group, such as phenylene, naphthylene, or a halogenated arylene group (wherein the halogen is selected from fluorine, chlorine, bromine), such as a halogenated phenylene group, and R ⁶ is -COOR ⁷ , C≡CH, C≡N; Also preferably, R's are the same or different, independently selected from -(CH ₂ ) _x' -R ⁵ -R ⁶ , where x' is 0 or 1; R ⁶ is -COOR ⁷ , -COR ⁷ ; R ⁷ is methyl or ethyl; Also preferably, R's are the same or different, and are independently selected from one of the following eight groups: Wherein, the upper side is the connection site. 4. The fluorescent sensor array according to any one of claims 1-3, characterized in that, Preferably, R is selected from C _3-10 straight chain or branched chain alkyl, (CH ₂ ) _x -R ¹ -OR ² , -(CH ₂ ) _y -R ¹ -R ³ or -(CH ₂ ) _z -R ⁴ , wherein, x is 0, 1 or 2, y is 0, 1 or 2, z is an integer of 2-6, R ¹ is phenylene or naphthylene or halogenated phenylene, R ² is C _1-10 straight chain or branched chain alkyl, R ³ is -H, -CF ₃ , C _1-10 straight chain or branched chain alkyl or CF ₃ substituted C _1-10 straight chain or branched chain Alkyl, R ⁴ is -CF ₃ ; Also preferably, when R is selected from C _3-10 straight chain or branched chain alkyl, the branched chain alkyl is an asymmetric alkyl; Also preferably, R is selected from one of the following groups: In the above groups, the upper side of the structural formula is the linking point. 5. The fluorescent sensing array according to any one of claims 1-4, characterized in that, each material in the described organic fluorescent sensing material is composed of one as described in formula (I) Organic semiconductor nanowires or nanoribbons self-assembled by carbazole derivatives through π-π interactions. Preferably, each of the organic fluorescent sensing materials is a porous film with a network structure formed by self-assembly and weaving of the organic semiconductor nanowires or nanobelts. 6. The preparation method of the fluorescent sensor array described in any one of claim 1-5, described method comprises the steps: (1) first synthesize the described several carbazole derivatives with special functional groups, (2) then in the mixed solution of good solvent and poor solvent, obtain described several kinds of organic fluorescent sensing materials by the mode of self-assembly, (3) Apply the assembled fluorescent materials to different positions inside the same glass tube to obtain the sensing array. 7. The preparation method according to claim 6, characterized in that, when preparing the carbazole derivatives of n=3 in the formula (I), the step (1) specifically comprises: (1a) the compound shown in the formula (II) reacts with RX ' to prepare the compound shown in the formula (III); X in formula (II) 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); Formula (III) and The definition of R in RX' is the same as formula (I); (1b) Compound shown in _formula (III) reacts with R'B(OH) to prepare compound shown in formula (IV); In formula (IV) and R'B(OH) ₂ , the definition of R' is the same as formula (I); In formula (IV), the definition of R and X is the same as formula (III); (1c) reacting the compound shown in formula (III) with dipivaloyl diboron to prepare the compound shown in formula (V); In formula (V), the definition of R is the same as formula (I); (1d) react the compound shown in the formula (IV) with the compound shown in the formula (V) to obtain the carbazole derivative shown in the formula (I), wherein n=3; Wherein, the compound shown in the formula (IV) and the compound shown in the formula (V) The molar ratio of the compounds shown is 2.1:1 to 2.5:1 (for example, 2.2:1); When preparing the carbazole derivatives of 3<n≤40 in the formula (I), the step (1) specifically includes: (1a) the compound shown in the formula (II) reacts with RX ' to prepare the compound shown in the formula (III); X in formula (II) 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); Formula (III) and The definition of R in RX' is the same as formula (I); (1a') the compound shown in the formula (II') reacts with RX' to prepare the compound shown in the formula (III'); X in formula (II') 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); Formula (III The definition of R in ') and RX' is the same as formula (I); m is an integer of 2-38; (1b) Compound shown in _formula (III) reacts with R'B(OH) to prepare compound shown in formula (IV); In formula (IV) and R'B(OH) ₂ , the definition of R' is the same as formula (I); In formula (IV), the definition of R and X is the same as formula (III); (1c') Compound shown in formula (III') reacts with bis-valeryl diboron to prepare compound shown in formula (V'); In formula (V'), the definition of R is the same as formula (I), and m is an integer of 2-38; (1d') The compound shown in the formula (IV) reacts with the compound shown in the formula (V') to obtain the carbazole derivative shown in the formula (I), wherein 3<n≤40; Wherein, the compound shown in the formula (IV) and The molar ratio of the compound represented by the formula (V') is 2.1:1 to 2.5:1 (for example, 2.2:1). 8. The preparation method according to claim 6 or 7, characterized in that, said step (2) comprises: dissolving the carbazole derivatives with different special functional groups obtained in step (1) in a good solvent, and then adding Poor solvent, stand still, the carbazole derivative shown in the formula (I) passes through the suspension of the organic fluorescent sensing material described in the self-assembly mode; Preferably, the step (2) further includes: after the suspension of the several organic fluorescent sensing materials is left to stand, take out the organic fluorescent sensing material located at the bottom of the preparation container, place it again in a poor solvent and shake to disperse evenly and repeatedly washing to obtain the organic fluorescent sensing material; Preferably, the step (3) includes: sequentially pouring the suspension of the organic fluorescent sensing material obtained in the step (2) into the same glass tube, waiting for the solvent to evaporate, and remembering the organic fluorescent sensing array; Preferably, the volume ratio (ml:ml) of the good solvent to the poor solvent is 1:3 to 1:10; Preferably, the good solvent is chlorinated alkanes and _C2-5 esters, such as dichloromethane, chloroform, 1,2-dichloroethane, ethyl acetate or methyl acetate; Preferably, the poor solvent is an alcoholic organic solvent or a cycloalkane, such as methanol, ethanol or cyclohexane. 9. The organic fluorescent sensing material according to any one of claims 1-5, especially the special network structure formed by the organic semiconductor nanowires or nanoribbons assembled with different functional group side chain carbazole derivatives The purpose of the porous membrane (with high specific surface area), is characterized in that these several sensing materials can be combined into a sensing array. 10. The purposes of the fluorescence sensor array described in any one of claim 1-5, it is characterized in that, for detecting and distinguishing solid explosives; Preferably, the fluorescent sensing array composed of organic fluorescent sensing materials that can perform fluorescence detection and distinction on several types of explosives can be used to detect and distinguish trace amounts of several types of explosives, and the trace amount is at the ng level When the several sensing materials are in contact with trace explosives (the explosives are preferably solid) steam, each material in the sensing array has different physical and chemical properties, and will occur to the same explosive Different forms of fluorescence changes, analyzing the fluorescence changes of several materials in several arrays for the same explosive, these changes are unique to each explosive, and thus can be used to actually detect and distinguish several types of explosives. Specifically, the obtained different sensing materials are coated in the quartz glass tube, and the vapor concentration of the explosive is increased by setting different temperatures by placing the explosive in a heat gun. When the organic fluorescent sensing materials with different substitution functional group side chains are in contact, the fluorescence of the different fluorescent sensing materials will change in different forms, and the fluorescence changes of several materials in several arrays to the same explosive are analyzed, and these changes affect each One type of explosive is unique, so as to achieve the purpose of detecting and distinguishing several types of explosives. Preferably, the classes of explosives are selected from RDX, Trinitrotoluene (TNT), Dinitrotoluene (DNT), Pentaerythritol Tetranitrate (PETN), Black Powder (S), Ammonium Nitrate (AN ) and 2,3-dinitro-2,3-dimethylbutane (DMNB).