CN107936946B - Preparation and application of organic fluorescence sensing array for distinguishing several types of explosives by fluorescence method - Google Patents

Preparation and application of organic fluorescence sensing array for distinguishing several types of explosives by fluorescence method Download PDF

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CN107936946B
CN107936946B CN201710967371.0A CN201710967371A CN107936946B CN 107936946 B CN107936946 B CN 107936946B CN 201710967371 A CN201710967371 A CN 201710967371A CN 107936946 B CN107936946 B CN 107936946B
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车延科
朱其建
熊伟
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Abstract

The invention relates to a fluorescent sensing array which is composed of a plurality of fluorescent sensing materials and can detect and distinguish five types of explosives, and a preparation method and application thereof. The fluorescent sensing array is made of organic fluorescent sensing materials, has typical P-type material characteristics and good luminous stability, and has a good effect of distinguishing explosives.

Description

Preparation and application of organic fluorescence sensing array for distinguishing several types of explosives by fluorescence method
Technical Field
The invention belongs to a fluorescent sensing array composed of organic semiconductor fluorescent nano materials, and particularly relates to a sensing array based on the design, synthesis and assembly of several P-type semiconductor materials of carbazole molecules and the selective differentiation of several types of explosives according to the fluorescent response change difference of the sensing array.
Background
The explosives have great threats to personal safety, national safety and natural environment. Therefore, researchers do a lot of work on the detection research of explosives, and if the explosives can be distinguished while being detected, the detection method is significant in anti-terrorism. Conventional explosives can be broadly classified into the following categories: nitroalkanes (DMNB), nitroaromatics (DNT, TNT), nitroamines (RDX), nitroesters (PETN), black powder (S), peroxides (TATP), and the like. The methods for explosive detection discrimination are currently less. As a widely applied distinguishing means, the method adopts several types of materials to assemble a sensing array, such as a colorimetric sensing array, and has made great progress in distinguishing volatile organic compounds, toxins and the like together with an auxiliary analysis method. The sensing array may also serve as a means to distinguish explosives well.
The fluorescence sensing array distinguishes explosives based on detecting explosives by fluorescence. The main principle of detecting and distinguishing explosives by a fluorescence method is that several fluorescent molecular materials forming a sensing array and the explosives generate different fluorescence change signals under different degrees of physicochemical action, and then the signals are analyzed to achieve the purpose of distinguishing. First, each class of explosive molecule has different chemical properties. For example, nitroaromatic explosives (DNT, TNT), which have high vapor pressure and relatively good volatility; the nitro group on the aromatic ring has strong electron-withdrawing capability, reduces the LUMO energy of molecules, has the particularity of the aromatic ring, and has strong bonding force with fluorescent molecules, so that the explosives are easy to detect and have more researches. Nitro-amine (RDX) and nitro-ester (PETN) explosives have low vapor pressure and poor volatility, and these molecules have poor electron donating ability and are relatively difficult to detect. But S and peroxide explosives are difficult to detect because of no chromophore. Therefore, it is very difficult to distinguish multiple types of explosives by using as few sensor arrays as possible and using simple analysis.
At present, the array distinguishing method in the existing report can distinguish fewer explosive species, and more explosive species do not exceed three types. And the sensing arrays have complex composition and high manufacturing cost, and a complicated analysis method is needed in the distinguishing process. This obviously does not meet the practical requirements. The simple sensing array for distinguishing multiple types of explosives is challenging for researchers.
Disclosure of 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 highly sensitive fluorescence detection discrimination on several types of explosives.
The invention also aims to provide a preparation method of a plurality of organic fluorescence sensing materials which are assembled into a sensing array capable of carrying out high-sensitivity fluorescence detection distinguishing on a plurality of explosives.
It is a further object of the present invention to provide the use of sensor arrays assembled from several classes of organic fluorescent sensing materials that can have high sensitivity fluorescence detection discrimination for several classes of explosives.
The core purpose of the invention is to prepare a fluorescence sensing array which can carry out high-sensitivity fluorescence detection distinguishing on several types of explosives, and the sensing array is formed by combining several different organic fluorescence sensing materials. The materials combined into the sensing array are a series of P-type organic fluorescent sensing materials based on carbazole molecules, each material of the materials is a structure of carbazole derivatives with different side chains synthesized by changing the side chains and the polymerization degree of the carbazole molecules, a plurality of one-dimensional organic semiconductor nanowires or nanobelts are obtained by a self-assembly method, and the sensing array assembled by the organic fluorescent sensing materials and capable of carrying out high-sensitivity fluorescent detection and distinguishing on a plurality of types of explosives is prepared by a manufacturing process. The materials combined into the sensing array in the invention, namely, a plurality of nano wires or nano belts assembled by molecules have larger specific surface area and more surface pores, are beneficial to the better interaction of the vapor of the detected explosive on the surface of the nano wires or nano belts through adsorption and diffusion, different fluorescence responses are generated due to different surface physicochemical properties of the materials, and the response of the materials in the array to each type of explosive is unique, so that a fingerprint-like identification mark can be formed, and the explosives can be distinguished. The organic fluorescent sensing materials obtained by self-assembling several side chain carbazole molecule derivatives with different substituent groups in the sensing array have different appearances, namely nanobelts and nanowires, generate different fluorescent responses to different explosives, and when the sensing array is used, a distinguishing effect can be achieved according to different fluorescent responses. Therefore, the fluorescence sensing array can be used as an organic fluorescence sensing array for detecting and distinguishing several types of explosives.
The invention is realized by the following technical scheme:
a fluorescence sensing array assembled by organic fluorescence sensing materials is characterized in that the fluorescence sensing array is formed by sequentially arranging more than two organic fluorescence sensing materials capable of carrying out fluorescence monitoring and distinguishing on several types of explosives, and each organic fluorescence material is obtained by self-assembling carbazole derivatives shown in a formula (I) through pi-pi interaction:
Figure BDA0001436735370000031
in the formula (I), the compound has the following structure,
r' are identical or different and are independently selected from- (CH)2)x’-R5-R6Wherein x' is 0, 1 or 2, R5Is arylene or haloarylene, R6Is H, -COOR7、-COR7、C2-6Alkynyl, C.ident.N or C3-6Alkyl radical, R7Is H, C1-4Alkyl groups of (a);
n is an integer of 3 to 40;
r is selected from C1-10Straight or branched alkyl, - (CH)2)x-R1-O-R2、-(CH2)y-R1-R3Or- (CH)2)z-R4，
Wherein x is 0, 1 or 2, y is 0, 1 or 2, z is an integer of 1 to 9, R1Is arylene or haloarylene, R2Is C1-10Straight or branched alkyl of R3is-H, -CHF2、-CF3、C1-10Straight or branched alkyl of (2), C3-10Cycloalkyl group of (1), by CHF2Or CF3Substituted C1-10Straight or branched alkyl of (2), C3-10Cycloalkyl group of (1), by CHF2Or CF3Substituted C3-10Cycloalkyl of, R4is-CHF2、-CF3。
Preferably, the fluorescence sensing array is formed by sequentially arranging 2-6 organic fluorescence sensing materials.
According to the 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 invention, in the fluorescence sensing array, the length of each organic fluorescence sensing material is 3mm-20mm, and is adjustable, preferably 8-10 mm; the distance between two adjacent materials is 5mm-50mm, and is adjustable, preferably 15-20 mm.
Further preferably, R' phaseAre identical or different and are independently selected from- (CH)2)x’-R5-R6X' is 0 or 1; r5Is a halogenated arylene (wherein halogen is selected from fluorine, chlorine or bromine), such as a halogenated phenylene, an arylene, such as a phenylene or naphthylene; r6Is C ≡ CH, C ≡ C-CH3Or C ≡ N;
also preferably, R', equal or different, are chosen, independently of one another, from- (CH)2)x’-R5-R6X' is 0 or 1; r6is-COOR7、-COR7；R7Is methyl or ethyl;
also preferably, R', which are identical or different, are independently from each other selected from one of the following eight groups:
Figure BDA0001436735370000041
wherein the upper side is the attachment site.
Preferably, R is selected from C3-10Straight or branched alkyl of (CH)2)x-R1-O-R2、-(CH2)y-R1-R3Or- (CH)2)z-R4，
Wherein x is 0, 1 or 2, y is 0, 1 or 2, z is an integer of 2 to 6, R1Is phenylene or naphthylene or halophenylene, R2Is C1-10Straight or branched alkyl of R3is-H, -CF3、C1-10Straight or branched alkyl or CF3Substituted C1-10Straight or branched alkyl of R4is-CF3。
Preferably, R is selected from C3-10The branched alkyl group of (a), which is an asymmetric alkyl group.
Also preferably, R is selected from one of the following groups:
Figure BDA0001436735370000051
in the above groups, the upper side of the structural formula is the attachment site.
According to the fluorescence sensing array, each material in the organic fluorescence sensing materials is an organic semiconductor nanowire or nanoribbon which is obtained by self-assembling the carbazole derivative shown in the formula (I) through pi-pi interaction.
Further, each of the organic fluorescent sensing materials is a porous membrane with a net structure formed by self-assembly weaving of the organic semiconductor nanowires or the nanobelts.
The invention also provides a preparation method of the fluorescence sensing array, which is characterized by comprising the following steps:
(1) synthesizing the carbazole derivative with special functional groups shown in the formula (I),
Figure BDA0001436735370000061
wherein each substituent is as previously defined;
(2) in the mixed solution of the good solvent and the poor solvent, the organic fluorescence sensing materials are obtained by a self-assembly mode,
(3) and respectively coating the assembled several fluorescent materials on different positions of the inner side of the same glass tube to obtain the sensing array.
According to the invention, in step (1):
when preparing the carbazole derivative of formula (I) in which n ═ 3, the step (1) specifically includes:
(1a) reacting the compound shown in the formula (II) with RX' to obtain a compound shown in a formula (III);
Figure BDA0001436735370000062
x in formula (II) and formula (III), which are identical or different, are independently selected from halogen (e.g. Br, I); x 'in RX' is selected from halogen (e.g., Br, I); r in formula (III) and RX' is as defined for formula (I);
(1b) a compound of formula (III) with R' B (OH)2Reacting to obtain a compound shown as a formula (IV);
Figure BDA0001436735370000063
formula (IV) and R' B (OH)2Wherein R' is as defined for formula (I); in the formula (IV), R and X are as defined in the formula (III);
(1c) reacting the compound shown in the formula (III) with bis (valeryl) diboron to obtain a compound shown in a formula (V);
Figure BDA0001436735370000071
in the formula (V), R is as defined in the formula (I);
(1d) reacting a compound represented by formula (IV) with a compound represented by formula (V) to obtain a carbazole derivative represented by formula (I), wherein n is 3; wherein the molar ratio of the compound shown in the formula (IV) to the compound shown in the formula (V) is 2.1: 1-2.5: 1 (for example, 2.2: 1);
when preparing the carbazole derivative with 3< n ≦ 40 in the formula (I), the step (1) specifically comprises:
(1a) reacting the compound shown in the formula (II) with RX' to obtain a compound shown in a formula (III);
Figure BDA0001436735370000072
x in formula (II) and formula (III), which are identical or different, are independently selected from halogen (e.g. Br, I); x 'in RX' is selected from halogen (e.g., Br, I); r in formula (III) and RX' is as defined for formula (I);
(1a ') reacting the compound represented by the formula (II') with RX 'to obtain a compound represented by the formula (III');
Figure BDA0001436735370000073
x in formula (II ') and formula (III'), which are identical or different, are independently selected from halogen (e.g. Br, I); x 'in RX' is selected from halogen (e.g., Br, I); r in the formulae (III ') and RX' is as defined for formula (I); m is an integer from 2 to 38;
(1b) a compound of formula (III) with R' B (OH)2Reacting to obtain a compound shown as a formula (IV);
Figure BDA0001436735370000081
formula (IV) and R' B (OH)2Wherein R' is as defined for formula (I); in the formula (IV), R and X are as defined in the formula (III);
(1c ') reacting the compound shown in the formula (III ') with bis (valeryl) diboron to obtain a compound shown in the formula (V ');
Figure BDA0001436735370000082
in the formula (V'), R is as defined in formula (I), and m is an integer of 2 to 38;
(1d ') reacting 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 3< n < 40; wherein the molar ratio of the compound represented by the formula (IV) to 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 with different special functional groups obtained in the step (1) and shown in the formula (I) in a good solvent, then adding a poor solvent, standing, and allowing the carbazole derivatives shown in the formula (I) to pass through a suspension of the organic fluorescent sensing material in a self-assembly mode;
preferably, the step (2) further comprises: standing the suspension of the organic fluorescent sensing materials, taking out the organic fluorescent sensing material at the bottom of the preparation container, putting the organic fluorescent sensing material in a poor solvent again, shaking up, dispersing 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: 3-1: 10;
preferably, the good solvent is selected from chloroalkanes and C2-5Esters, 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: and (3) sequentially injecting the suspensions of the organic fluorescent sensing materials obtained in the step (2) into the same glass tube, and recording to obtain the organic fluorescent sensing array after the solvent is volatilized to be dry.
The fluorescence sensing array is composed of a porous membrane material with a net structure formed by a plurality of organic semiconductor nanowires or nanobelts, the material has high specific surface area, has different fluorescence responses to different explosives, and can detect and distinguish the explosives according to the fluorescence responses through analysis.
The invention also provides application of the fluorescence sensing array in distinguishing several types of explosives, wherein the fluorescence sensing array is composed of several organic fluorescence sensing materials.
According to the invention, the fluorescence sensing array can perform rapid fluorescence detection discrimination on several types of explosives.
According to the invention, the fluorescence sensing array can be used for detecting and distinguishing solid explosives.
According to the application of the invention, the fluorescence sensing array can be used for detecting and distinguishing trace amounts of several types of explosives, wherein the trace amount is in the ng or sub-ng grade.
In the invention, when the fluorescence sensing array is contacted with trace explosive (the explosive is preferably solid) steam, because each fluorescent material has different substituted functional group side chains and different morphologies and has different surface physicochemical properties, different forms of fluorescence changes can occur, and the fluorescence sensing array can be used for actually detecting and distinguishing several types of explosives by analyzing signals of the fluorescence changes.
The obtained different sensing materials are coated in a quartz glass sheet tube in a spinning mode, explosives are placed in a heating gun, the steam concentration of the explosives is improved by setting different temperatures, when different explosive steams are in contact with organic fluorescent sensing materials with different substituted functional group side chains, the fluorescence of the different fluorescent sensing materials can be changed in different forms, and the purpose of detecting and distinguishing the explosives is achieved by analyzing fluorescence change signals.
The explosives are selected from hexogen (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 body of the composition material of the fluorescence sensing array is a typical P-type semiconductor fluorescence sensing material. According to the invention, the substituted functional groups and the polymerization degree of the main body are designed and modified, so that when the formed designed organic fluorescence sensing materials interact with high-temperature steam of nitro-containing explosives, electron transfer or physical adsorption with different intensities can occur to different degrees, fluorescence changes of different forms of the organic fluorescence sensing materials are caused, the fluorescence response of the material 1 is named as Q1, the fluorescence response of the material 2 is named as Q2, and the fluorescence response of the material N is named as QN. The different forms of fluorescence change arrays thus obtained are different and unique for each type of explosive. Therefore, the sensing array composed of several different organic fluorescent sensing materials can perform rapid fluorescence detection discrimination on several types of explosives.
It should be noted that the several types of explosives described in the present invention are distinguished according to their categories, and one type of explosive may contain one or more types of explosives.
The invention has the beneficial effects that:
the organic fluorescence sensing material adopted by the invention is obtained by self-assembling carbazole derivatives through pi-pi interaction, different forms of fluorescence changes of different explosives can be formed by modifying specific substituted functional group side chains and polymerization degrees on a main body, and a sensing array is formed by assembling a plurality of organic fluorescence sensing materials with different fluorescence changes, so that a fluorescence change array specific to each explosive is formed, and the fluorescence distinguishing of the explosives is realized.
The sensing array can detect and distinguish several types of explosives at ng level, the detection and distinguishing sensitivity is high, and the structure and the operation of the sensing array are simpler and more convenient. Through design, the sensing array can be further made into portable equipment capable of rapidly detecting and distinguishing several types of explosives, and the portable equipment is applied and serves the society, so that the portable equipment has significant work and has a far-reaching application and development prospect.
The invention also provides a simple and efficient preparation method of the organic fluorescent sensing materials in the sensing array, the synthetic route of the method is simple, large-scale preparation is convenient, and the nanowire growth method is simple and rapid.
Drawings
FIG. 1 is a schematic diagram of a fluorescence sensor array according to the present invention.
FIG. 2 shows the nuclear magnetic data spectrum of the carbazole derivative of example 1 of the present invention in which R is n-octane and n is 3.
FIG. 3 is a graph showing mass spectrum data of a carbazole derivative of example 1 of the present invention in which R is n-octane and n is 3.
FIG. 4 shows nuclear magnetic data of carbazole derivatives of example 2 of the present invention, wherein R is benzyl and n is 3.
FIG. 5 is an SEM image of an organic semiconductor nanowire having an ultrasensitive fluorescent response, which is constructed from a carbazole derivative in which R is n-octane and n is 3 according to example 1 of the present invention.
Fig. 6 is a fluorescence curve diagram for detecting TNT of a sensor array composed of a porous membrane having a mesh structure formed by self-assembly knitting of organic semiconductor nanowires with ultrasensitive fluorescence response, wherein R is n-octane and n is 3, and the porous membrane having a mesh structure formed by self-assembly knitting of organic semiconductor nanowires with ultrasensitive fluorescence response, wherein R is isobutyl and n is 3, and the porous membrane is formed by self-assembly knitting of organic semiconductor nanowires with ultrasensitive fluorescence response, in example 1 of the present invention. 1.1< Q2/Q1< 2.
Fig. 7 is a fluorescence detection curve diagram of DNT of a sensor array comprising a porous membrane having a mesh structure formed by self-assembly knitting of organic semiconductor nanowires having an ultrasensitive fluorescence response, wherein R is n-octane and n is 3 and constructed by carbazole derivatives of embodiment 1 of the present invention, and a porous membrane having a mesh structure formed by self-assembly knitting of organic semiconductor nanowires having an ultrasensitive fluorescence response, wherein R is isobutyl and n is 3 and constructed by carbazole derivatives of embodiment 2 of the present invention. 1.1< Q2/Q1< 2.
Fig. 8 is a fluorescence detection curve diagram of S for a sensor array comprising a porous membrane having a mesh structure formed by self-assembly knitting of organic semiconductor nanowires having an ultrasensitive fluorescence response, wherein R is n-octane and n is 3 and constructed by carbazole derivatives of embodiment 1 of the present invention, and a porous membrane having a mesh structure formed by self-assembly knitting of organic semiconductor nanowires having an ultrasensitive fluorescence response, wherein R is isobutyl and n is 3 and constructed by carbazole derivatives of embodiment 2 of the present invention. 2.1< Q2/Q1< 4.5.
Fig. 9 is a fluorescence detection curve diagram of RDX for a sensor array composed of a porous membrane with a mesh structure formed by self-assembly knitting of organic semiconductor nanowires with ultrasensitive fluorescence response, wherein R is n-octane and n is 3 and constructed by carbazole derivatives of embodiment 1 of the present invention, and a porous membrane with a mesh structure formed by self-assembly knitting of organic semiconductor nanowires with ultrasensitive fluorescence response, wherein R is isobutyl and n is 3 and constructed by carbazole derivatives of embodiment 2 of the present invention. 2.1< Q1/Q2< 4.0.
Fig. 10 is a fluorescence curve diagram for detection of PETN of a sensor array composed of a porous membrane having a mesh structure formed by self-assembly knitting of organic semiconductor nanowires with ultrasensitive fluorescence response, which is constructed by carbazole derivatives with R being n-octane and n being 3 in example 1 of the present invention, and a porous membrane having a mesh structure formed by self-assembly knitting of organic semiconductor nanowires with ultrasensitive fluorescence response, which is constructed by carbazole derivatives with R being isobutyl and n being 3 in example 2 of the present invention. 2.1< Q1/Q2< 4.0.
Fig. 11 is a fluorescence detection curve diagram of a DMNB, which is a sensor array including a porous membrane having a mesh structure formed by self-assembly knitting of organic semiconductor nanowires having an ultrasensitive fluorescence response, the porous membrane being constructed by R of n-octane and n of 3 carbazole derivatives in example 1 of the present invention, and the porous membrane having a mesh structure formed by self-assembly knitting of organic semiconductor nanowires having an ultrasensitive fluorescence response. The fluorescence response was recovered by nearly 100%.
Fig. 12 is a fluorescence detection curve diagram of AN array sensor comprising a porous membrane having a mesh structure formed by self-assembly knitting of organic semiconductor nanowires having AN ultrasensitive fluorescence response, wherein R is n-octane and n is 3, and a porous membrane having a mesh structure formed by self-assembly knitting of organic semiconductor nanowires having AN ultrasensitive fluorescence response, wherein R is isobutyl and n is 3, and the porous membrane is formed by self-assembly knitting of organic semiconductor nanowires having AN ultrasensitive fluorescence response, in example 1 of the present invention. 1.1< Q1/Q2< 2.0.
Fig. 13 shows that the fluorescent response of the porous membrane with a mesh structure formed by self-assembly knitting of organic semiconductor nanowires with ultrasensitive fluorescent response, which is constructed by carbazole derivatives with n being 3, to four types of explosives is named as Q1 in example 1 of the present invention, the fluorescent response of the sensor array with a mesh structure formed by self-assembly knitting of organic semiconductor nanowires with ultrasensitive fluorescent response, which is constructed by carbazole derivatives with n being 3, to four types of explosives is named as Q2 in example 2 of the present invention, and the graphs are made according to Q1/Q2 and Q2/Q1.
Fig. 14 is a fluorescence detection curve diagram of NM of a sensor array comprising a porous membrane having a mesh structure formed by self-assembly knitting of organic semiconductor nanowires having an ultrasensitive fluorescence response, wherein R is n-octane and n is 3, in example 1 of the present invention, and a porous membrane having a mesh structure formed by self-assembly knitting of organic semiconductor nanowires having an ultrasensitive fluorescence response, wherein R is isobutyl and n is 3, in example 2 of the present invention. The fluorescence response was recovered by nearly 100%.
Detailed Description
As described above, the present invention discloses a method for preparing an organic fluorescent sensing material that can perform high-sensitivity fluorescence detection differentiation on several types of explosives, and in a preferred embodiment of the present invention, a carbazole derivative of formula (I) where n ═ 3 is prepared, and the step (1) specifically includes:
(1a) reacting the compound shown in the formula (II) with RX' to obtain a compound shown in a formula (III);
Figure BDA0001436735370000131
x in formula (II) and formula (III), which are identical or different, are independently selected from halogen (e.g. Br, I); x 'in RX' is selected from halogen (e.g., Br, I); r in formula (III) and RX' is as defined for formula (I);
(1b) a compound of formula (III) with R' B (OH)2Reacting to obtain a compound shown as a formula (IV);
Figure BDA0001436735370000132
formula (IV) and R' B (OH)2Wherein R' is as defined for formula (I); in the formula (IV), R and X are as defined in the formula (III);
(1c) reacting the compound shown in the formula (III) with bis (valeryl) diboron to obtain a compound shown in a formula (V);
Figure BDA0001436735370000133
in the formula (V), R is as defined in the formula (I);
(1d) reacting a compound represented by formula (IV) with a compound represented by formula (V) to obtain a carbazole derivative represented by formula (I), wherein n is 3; wherein the molar ratio of the compound represented by the formula (IV) to the compound represented by the formula (V) is 2.1:1 to 2.5:1 (for example, 2.2: 1).
In another preferred embodiment of the present invention, a carbazole derivative of formula (I) wherein 3< n.ltoreq.40 is prepared, said step (1) comprising in particular:
(1a) reacting the compound shown in the formula (II) with RX' to obtain a compound shown in a formula (III);
Figure BDA0001436735370000141
x in formula (II) and formula (III), which are identical or different, are independently selected from halogen (e.g. Br, I); x 'in RX' is selected from halogen (e.g., Br, I); r in formula (III) and RX' is as defined for formula (I);
(1a ') reacting the compound represented by the formula (II') with RX 'to obtain a compound represented by the formula (III');
Figure BDA0001436735370000142
x in formula (II ') and formula (III'), which are identical or different, are independently selected from halogen (e.g. Br, I); x 'in RX' is selected from halogen (e.g., Br, I); r in the formulae (III ') and RX' is as defined for formula (I); m is an integer from 2 to 38;
(1b) a compound of formula (III) with R' B (OH)2Reacting to obtain a compound shown as a formula (IV);
Figure BDA0001436735370000143
formula (IV) and R' B (OH)2Wherein R' is as defined for formula (I); in the formula (IV), R and X are as defined in the formula (III);
(1c ') reacting the compound shown in the formula (III ') with bis (valeryl) diboron to obtain a compound shown in the formula (V ');
Figure BDA0001436735370000151
in the formula (V'), R is as defined in formula (I), and m is an integer of 2 to 38;
(1d ') reacting 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 3< n < 40; wherein the molar ratio of the compound represented by the formula (IV) to 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 (1 a'), the reaction is carried out in a solvent. The solvent is an organic solvent capable of dissolving the compound represented by formula (II) or formula (II'), for example, an amide compound, and specifically, may be selected from N, N-dimethyl-formamide.
In the step (1a) or (1 a'), the reaction is carried out at a temperature of-10 to 10 ℃, preferably-5 to 5 ℃.
In the 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 shown in the formula (II) to the catalyst is 1: 1.1-1: 1.3, preferably 1: 1.2.
In the step (1 a'), the reaction is carried out under the action of a catalyst. The catalyst is for example sodium hydride. The equivalent ratio of the compound of formula (II') to the catalyst is from 1 (m +0.1) to 1 (m +0.3), preferably 1 (m +0.2), m being an integer from 2 to 38.
In the step (1a), the equivalent ratio of the compound of formula (II) to RX' is 1.1.2-1: 1.5, preferably 1: 1.3.
In step (1a '), the equivalent ratio of the compound of formula (II ') to RX ' is 1 (m +0.2) to 1 (m +0.5), preferably 1 (m +0.3), and m is an integer of 2 to 38.
In a preferred embodiment, a carbazole derivative of formula (I) where n ═ 3 is prepared, and the step (1a) is specifically: dissolving 1 equivalent of 2, 7-dibromocarbazole in N, N-dimethyl-formamide to prepare a solution with the concentration of 1g/30ml, placing the solution in an ice bath at 0 ℃, slowly adding 1.2 equivalents of sodium hydride solid, continuously stirring for half an hour, slowly adding 1.5 equivalents of 1-bromooctane, 2-bromobutane, 4-trifluoromethyl benzyl bromide, benzyl bromide or 4-methoxy benzyl bromide, reacting at room temperature overnight, and performing column chromatography to obtain a product.
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 the formula (III), and is, for example, an epoxy compound, and specifically may be 1, 4-dioxane.
In step (1b) above, the compound of formula (III) is reacted with R' B (OH)2Is 1:1.
In the above step (1b), the reaction is carried out in a catalyst system comprising tetrakis (triphenylphosphine) palladium and cesium carbonate. The amount of tetrakis (triphenylphosphine) palladium added is 5 to 15% by equivalent and the amount of cesium carbonate added is 2.5 to 3.5 by equivalent to 1 by equivalent of the compound of formula (III).
In the step (1b), the reaction is carried out under the protection of inert gas, the reaction temperature is 70-90 ℃, and the reaction time is 6-8 hours.
In a preferred embodiment, the step (1b) is specifically: (1b) taking 1 equivalent of the product obtained in the step (1a), dissolving the product in 1, 4-dioxane to prepare a solution with the concentration of 1g/20ml, adding 1 equivalent of p-methoxycarbonylphenylboronic acid, 10% equivalent of tetrakis (triphenylphosphine) palladium and 3 equivalents of cesium carbonate, reacting for 6 hours at 80 ℃ under the protection of argon, and then carrying out column chromatography to obtain the product.
In the above step (1c) or (1 c'), the reaction is carried out in a solvent. The solvent is an organic solvent capable of dissolving the compound represented by the formula (III) or the formula (III'), and is, for example, an epoxy compound, and specifically may be 1, 4-dioxane.
In the step (1c) or (1c '), the equivalent ratio of the compound of formula (III) or (III') to the bis-valeryl diboron is 1:4 to 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 ] dichloropalladium. The amount of potassium acetate added is 10 to 20 equivalents and the amount of [1,1 '-bis (diphenylphosphino) ferrocene ] palladium dichloride added is 5 to 15% equivalents with respect to 1 equivalent of the compound of formula (III) or (III').
In the step (1c) or (1 c'), the reaction is carried out under the protection of inert gas, the reaction temperature is 70-80 ℃, and the reaction time is 4-8 hours.
In a preferred embodiment, a carbazole derivative of formula (I) wherein n ═ 3 is prepared, and said step (1c) is specifically: taking 1 equivalent of the product obtained in the step (1a), adding 1, 4-dioxane to prepare a solution with the concentration of 1g/20ml, adding 5 equivalents of bis (valeryl) diboron, 14 equivalents of potassium acetate and 10% equivalents of [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride, reacting for 6 hours at the temperature of 80 ℃ under the protection of argon, and then carrying out column chromatography to obtain the product.
In the above step (1d) or (1 d'), the reaction is carried out in a solvent. The solvent is an organic solvent capable of dissolving the compounds represented by the formulae (VI), (V) and (V'), and is, for example, an aromatic hydrocarbon, and 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 (V') is 1: 2.2.
In the above step (1d) or (1 d'), the reaction is carried out in a catalyst system comprising tetrakis (triphenylphosphine) palladium and potassium carbonate. The amount of potassium carbonate added is 3 to 5 equivalents, and the amount of tetrakis (triphenylphosphine) palladium added is 5 to 15% equivalent, based on 1 equivalent of the compound of formula (III).
In the step (1d) or (1 d'), the reaction is carried out under the protection of inert gas, the reaction temperature is 70-90 ℃, and the reaction time is 12-48 hours.
In a preferred embodiment, a carbazole derivative of formula (I) wherein n ═ 3 is prepared, and said step (1d) is specifically: and (2) adding 1mmol and 2.2mmol of products obtained in the step (1c) and the step (1b) into 20ml of toluene solution, adding 10% of tetrakis (triphenylphosphine) palladium and 3 equivalents of potassium carbonate, reacting overnight at 80 ℃ under the protection of argon, and then carrying out column chromatography to obtain the product.
For further explanation of objects, aspects and advantages of the present invention, reference is made to the following detailed description of the invention, which is to be read in connection with the accompanying drawings. Those skilled in the art will appreciate that the present invention is not limited to the drawings and the following examples.
Example 1
A carbazole derivative having the following molecule 1, wherein R is a linear octyl group, R' is a 4-methoxycarbonylphenyl group, and n is 3, is prepared by the following method:
Figure BDA0001436735370000181
(1) dissolving 1g of 2, 7-dibromocarbazole in 30ml of N, N-dimethyl-formamide (DMF) solution, placing the solution in an ice bath at 0 ℃, slowly adding 1.2 equivalents of 74mg of sodium hydride solid, continuously stirring for half an hour, slowly adding 1.5 equivalents of 1-bromooctane, reacting at room temperature overnight, and performing column chromatography to obtain a product.
(2) And (2) adding 500mg of the product obtained in the step (1) into 20ml of 1, 4-dioxane solution, adding 5 equivalents of bis (valeryl diboron), 14 equivalents of potassium acetate and 10% equivalents of [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride, reacting for 6 hours at 80 ℃ under the protection of argon, and then carrying out column chromatography to obtain a product (TM-1).
(3) And (2) adding 500mg of the product obtained in the step (1) into 20ml of 1, 4-dioxane solution, adding 1 equivalent of p-methylcarbonylphenylboronic acid, 10% equivalent of tetrakis (triphenylphosphine) palladium and 3 equivalents of cesium carbonate, reacting for 6 hours at 80 ℃ under the protection of argon, and then carrying out column chromatography to obtain the product.
(4) Adding 1mmol and 2.2mmol of the products obtained in the step (2) and the step (3) into 20ml of toluene solution, adding 10% of tetrakis (triphenylphosphine) palladium and 3 equivalents of potassium carbonate, reacting overnight at 80 ℃ under the protection of argon, and performing column chromatography to obtain a product (molecule 1); the nuclear magnetic resonance data map is shown in FIG. 2; the mass spectra data are shown in figure 3.
(5) Dissolving the carbazole derivative (molecule 2) with p-methylcarbonylphenyl group, wherein n is 3, obtained in the step (4) in a good solvent, and then adding a poor solvent, wherein the good solvent is one of ethyl acetate, dichloromethane, chloroform or 1, 2-dichloroethane, the poor solvent is one of methanol, ethanol or cyclohexane, and the volume ratio of the good solvent to the poor solvent is 1: 3-1: 10; standing, and obtaining the organic semiconductor nanowire or nanobelt suspension with different fluorescence responses to several types of explosives by the carbazole derivative with the p-methyl carbonyl benzene in a self-assembly mode.
Example 2
The carbazole derivative with the following molecules 2, R is benzyl, R' is 4-methoxycarbonylphenyl and n is 3 is prepared by the following method:
Figure BDA0001436735370000191
(1) dissolving 1g of 2, 7-dibromocarbazole in 30ml of N, N-dimethyl-formamide (DMF) solution, placing the solution in an ice bath at 0 ℃, slowly adding 1.2 equivalents of 74mg of sodium hydride solid, continuously stirring for half an hour, slowly adding 1.5 equivalents of benzyl bromide, reacting at room temperature overnight, and then carrying out column chromatography to obtain the product.
(2) And (2) adding 500mg of the product obtained in the step (1) into 20ml of 1, 4-dioxane solution, adding 5 equivalents of bis (valeryl diboron), 14 equivalents of potassium acetate and 10% equivalents of [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride, reacting for 6 hours at 80 ℃ under the protection of argon, and then carrying out column chromatography to obtain a product (TM-1).
(3) And (2) adding 500mg of the product obtained in the step (1) into 20ml of 1, 4-dioxane solution, adding 1 equivalent of p-methoxycarbonylphenylboronic acid, 10% equivalent of tetrakis (triphenylphosphine) palladium and 3 equivalents of cesium carbonate, reacting for 6 hours at 80 ℃ under the protection of argon, and then carrying out column chromatography to obtain the product.
(4) Adding 1mmol and 2.2mmol of the products obtained in the step (2) and the step (3) into 20ml of toluene solution, adding 10% of tetrakis (triphenylphosphine) palladium and 3 equivalents of potassium carbonate, reacting overnight at 80 ℃ under the protection of argon, and performing column chromatography to obtain a product (molecule 2); mass spectrometry data MALDI-TOF (m/z) ═ 1035.4; the nuclear magnetic resonance data map is shown in fig. 4.
(5) Dissolving the carbazole derivative with n being 3 obtained in the step (4) in a good solvent, and adding a poor solvent, wherein the good solvent is one of dichloromethane, chloroform or 1, 2-dichloroethane, the poor solvent is one of methanol, ethanol or cyclohexane, and the volume ratio of the good solvent to the poor solvent is 1: 2-1: 15; standing, and obtaining the organic semiconductor nanowire suspension with fluorescent response to several types of explosives by the carbazole derivative in a self-assembly mode.
Example 3
Respectively taking out a sample at the bottom of a container from suspension prepared by the carbazole derivative with 4-cyanophenyl in the step (5) in the example 1 by using a liquid transfer gun, placing the sample on the surface of a clean silicon wafer, placing the sample in an ion sputtering machine (Leica) after a poor solvent is completely volatilized, and vacuumizing until the vacuum degree is 10-4pa followed by the start of surface sputtering of platinum particles 120 s. The silicon wafer was taken out and placed on a scanning electron microscope (Hitachi S8010) for observation of its morphology. As can be observed in fig. 5 a, b and c, the one-dimensional organic semiconductor nanobelts self-assemble and weave into a unique net-shaped porous structure, which provides a special fluorescent response signal for detection differentiation.
Example 4
After the suspensions obtained in the step (5) of the example 1 and the step (5) of the example 2 are stood for 24 hours, the films at the bottom of the container are taken out and respectively coated at different positions in the same quartz glass tube in sequence, and the fluorescent sensing array containing two materials is prepared. The porous membrane coated inside the quartz glass tube was excited using a 380 nm excitation light source. And (3) respectively transferring 0.3ng, 0.5ng and 0.8ng of TNT (trinitrotoluene) into a heating gun by using a liquid transfer gun by using a solid explosive detector, setting the heating temperature to be 170 ℃, blowing TNT steam with different concentrations to the surface of the porous membrane, and detecting the fluorescence change shown in the figure 6 when the three concentrations are obtained.
Example 5
Using the same procedure as in example 4 except that the test substance was replaced with 0.3ng, 0.5ng, and 0.8ng of DNT, the results of the measurement showed changes in fluorescence as shown in FIG. 7 at the three concentrations.
Example 6
Using the same method as in example 4 except that the analytes were replaced with 0.2ng, 0.5ng, and 1ng S, the change in fluorescence as shown in FIG. 8 was observed at the three concentrations.
Example 7
In the same manner as in example 4, the analytes were changed to 0.1ng, 0.2ng and 0.5ng RDX, and the fluorescence change was observed at the three concentrations as shown in FIG. 9.
Example 8
In the same manner as in example 4, the analytes were changed to 0.5ng,1ng, and 2ng of PETN, and the fluorescence change as shown in FIG. 10 was observed at the three concentrations.
Example 9
In the same manner as in example 4, the samples were changed to 30ng, 50ng and 80ng of DMNB, and the fluorescence change as shown in FIG. 11 was observed at the three concentrations.
Example 10
In the same manner as in example 4, the samples were changed to 10ng, 20ng and 30ng AN, and the fluorescence change was observed at the three concentrations as shown in FIG. 12.
The fluorescence response changes of the eight explosives are subjected to pattern analysis by using a sensing array consisting of two organic fluorescent derivatives (material 1 and material 2) obtained by self-assembling the carbazole derivatives with different functional group side chains in example 1 and example 2. The fluorescence response of the material 1 is named as Q1, the fluorescence response of the material 2 is Q2, and the change of the fluorescence response of the sensing array to each type of explosive is unique according to the ratio analysis of Q1/Q2 and Q2/Q1 as shown in FIG. 13. Analysis shows that the fluorescence response of the two materials to DMNB and NM is approximately 100% recovered after fluorescence quenching (as shown in FIG. 14), while the two materials are not recovered to other explosives, so that the five types of explosives are distinguished. Therefore, which type of explosive is detected can be determined from the response of the sensing array composed of the two materials.
Example 11
(1) Dissolving 1g of 2, 7-dibromocarbazole in 30ml of N, N-dimethyl-formamide (DMF) solution, placing the solution in an ice bath at 0 ℃, slowly adding 1.2 equivalents of 74mg of sodium hydride solid, continuously stirring for half an hour, slowly adding 1.5 equivalents of 1-bromooctane, reacting at room temperature overnight, and performing column chromatography to obtain a product.
(2) And (2) adding 500mg of the product obtained in the step (1) into 20ml of 1, 4-dioxane solution, adding 5 equivalents of bis (valeryl diboron), 14 equivalents of potassium acetate and 10% equivalents of [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride, reacting for 6 hours at 80 ℃ under the protection of argon, and then carrying out column chromatography to obtain a product (TM-1).
(3) And (2) adding 500mg of the product obtained in the step (1) into 20ml of 1, 4-dioxane solution, adding 1 equivalent of p-cyanobenzene boronic acid, 10% equivalent of tetrakis (triphenylphosphine) palladium and 3 equivalents of cesium carbonate, reacting for 6 hours at 80 ℃ under the protection of argon, and then carrying out column chromatography to obtain the product (TM-2).
(4) And (3) adding 1mmol and 2.2mmol of products obtained in the step (2) and the step (3) into 20ml of toluene solution, adding 10% of tetrakis (triphenylphosphine) palladium and 3 equivalents of potassium carbonate, reacting overnight at 80 ℃ under the protection of argon, and performing column chromatography to obtain the carbazole derivative with R being straight-chain octyl, R' being 4-cyanophenyl and n being 4 in the formula (I).
(5) Dissolving the carbazole derivative with 4-cyanophenyl group and n being 4 obtained in the step (4) in a good solvent, and adding a poor solvent, wherein the good solvent is one of ethyl acetate, dichloromethane, chloroform or 1, 2-dichloroethane, the poor solvent is one of methanol, ethanol or cyclohexane, and the volume ratio of the good solvent to the poor solvent is 1: 3-1: 10; standing, and obtaining the organic semiconductor nanowire or nanobelt suspension with different fluorescence responses to several types of explosives by the carbazole derivative with the 4-cyanophenyl group in a self-assembly mode.
Example 12
(1) Dissolving 1g of 2, 7-dibromocarbazole in 30ml of N, N-dimethyl-formamide (DMF) solution, placing the solution in an ice bath at 0 ℃, slowly adding 1.2 equivalents of 74mg of sodium hydride solid, continuously stirring for half an hour, slowly adding 1.5 equivalents of 1-bromooctane, reacting at room temperature overnight, and performing column chromatography to obtain a product.
(2) And (2) adding 500mg of the product obtained in the step (1) into 20ml of 1, 4-dioxane solution, adding 5 equivalents of bis (valeryl diboron), 14 equivalents of potassium acetate and 10% equivalents of [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride, reacting for 6 hours at 80 ℃ under the protection of argon, and then carrying out column chromatography to obtain a product (TM-1).
(3) And (2) adding 500mg of the product obtained in the step (1) into 20ml of 1, 4-dioxane solution, adding 1 equivalent of p-methylcarbonylphenylboronic acid, 10% equivalent of tetrakis (triphenylphosphine) palladium and 3 equivalents of cesium carbonate, reacting for 6 hours at 80 ℃ under the protection of argon, and then carrying out column chromatography to obtain a product (TM-2).
(4) And (3) adding 1mmol and 2.2mmol of products obtained in the step (2) and the step (3) into 20ml of toluene solution, adding 10% of tetrakis (triphenylphosphine) palladium and 3 equivalents of potassium carbonate, reacting overnight at 80 ℃ under the protection of argon, and performing column chromatography to obtain the carbazole derivative in the formula (I), wherein R is a straight-chain octyl group, R' is p-methylcarbonylphenyl group, and n is 4.
(5) Dissolving the carbazole derivative with p-methylcarbonylphenyl group, wherein n is 4, obtained in the step (4) in a good solvent, and then adding a poor solvent, wherein the good solvent is one of ethyl acetate, dichloromethane, chloroform or 1, 2-dichloroethane, the poor solvent is one of methanol, ethanol or cyclohexane, and the volume ratio of the good solvent to the poor solvent is 1: 3-1: 10; standing, and obtaining the organic semiconductor nanowire or nanobelt suspension with different fluorescence responses to several types of explosives by the carbazole derivative with the 4-methylcarbonylphenyl group in a self-assembly mode.
It was determined that the sensing array composed of two sensing materials with n being 4 has similar response changes to several types of explosives as the sensing array composed of the sensing materials in examples 1 and 2, and can also perform the function of fluorescence detection and discrimination to several types of explosives.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (26)

1. A fluorescence sensing array, comprising: the fluorescence sensing array is formed by sequentially arranging more than two organic fluorescence sensing materials which can carry out fluorescence monitoring and distinguishing on several types of explosives, and each organic fluorescence material is obtained by self-assembling a carbazole derivative shown as the formula (I) through pi-pi interaction:
Figure FDA0002287814920000011
in the formula (I), R' are the same or different and are independently selected from- (CH)2)x’-R5-R6Wherein x' is 0, 1 or 2, R5Is arylene or haloarylene, R6Is H, -COOR7、-COR7、C2-6Alkynyl, C.ident.N or C3-6Alkyl radical, R7Is H, C1-4Alkyl groups of (a); n is an integer of 3 to 40; r is selected from C1-10Straight or branched alkyl, - (CH)2)x-R1-O-R2、-(CH2)y-R1-R3Or- (CH)2)z-R4Wherein x is 0, 1 or 2, y is 0, 1 or 2, z is an integer of 1 to 9, R1Is arylene or haloarylene, R2Is C1-10Straight or branched alkyl of R3is-H, -CHF2、-CF3、C1-10Straight or branched chain alkyl of (1), CHF2Or CF3Substituted C1-10Straight or branched alkyl of (2), C3-10Cycloalkyl group of (1), by CHF2Or CF3Substituted C3-10Cycloalkyl of, R4is-CHF2、-CF3。
2. The fluorescence sensing array of claim 1, wherein: the fluorescence sensing array is formed by sequentially arranging 2-6 organic fluorescence sensing materials;
in the fluorescence sensing array, the length of each organic fluorescence sensing material is 3mm-20mm and is adjustable; the distance between two adjacent materials is 5mm-50mm and is adjustable.
3. The fluorescence sensing array of claim 2, wherein: in the fluorescence sensing array, the length of each organic fluorescence sensing material is 8-10 mm; the distance between two adjacent materials is 15-20 mm.
4. The fluorescence sensing array of claim 1 or 2, wherein: the R's are identical or different and are independently selected from- (CH)2)x’-R5-R6Wherein x' is 0 or 1, R5Is arylene, or haloarylene, R6is-COOR7、C≡CH、C≡N。
5. The fluorescence sensing array of claim 4, wherein: the arylene is selected from phenylene or naphthylene, the halogenated arylene is halogenated phenylene, and the halogen is selected from fluorine, chlorine or bromine.
6. The fluorescence sensing array of claim 1 or 2,the method is characterized in that: the R's are identical or different and are independently selected from- (CH)2)x’-R5-R6X' is 0 or 1; r6is-COOR7、-COR7；R7Is methyl or ethyl.
7. The fluorescence sensing array of claim 1 or 2, wherein: the R' is the same or different and is independently selected from one of the following eight groups:
Figure FDA0002287814920000021
wherein the upper side is the attachment site.
8. The fluorescence sensing array of any of claims 1-4,
r is selected from C3-10Straight or branched alkyl of (CH)2)x-R1-O-R2、-(CH2)y-R1-R3Or- (CH)2)z-R4Wherein x is 0, 1 or 2, y is 0, 1 or 2, z is an integer of 2 to 6, R1Is phenylene or naphthylene or halophenylene, R2Is C1-10Straight or branched alkyl of R3is-H, -CF3、C1-10Straight or branched alkyl or CF3Substituted C1-10Straight or branched alkyl of R4is-CF3。
9. The fluorescence sensing array of claim 8, wherein R is selected from C3-10When the alkyl group is a linear or branched alkyl group, the branched alkyl group is an asymmetric alkyl group.
10. The fluorescence sensing array of claim 8, wherein R is selected from one of the following groups:
Figure FDA0002287814920000031
Figure FDA0002287814920000041
in the above groups, the upper side of the structural formula is the attachment site.
11. A fluorescence sensing array according to any of claims 1-10, wherein each of said organic fluorescence sensing materials is an organic semiconductor nanowire or nanoribbon self-assembled by pi-pi interaction from a carbazole derivative according to said formula (I).
12. The fluorescence sensing array of claim 11, wherein each of said organic fluorescence sensing materials is a porous membrane with a network structure formed by self-assembly weaving of said organic semiconductor nanowires or nanobelts.
13. A method of making a fluorescence sensing array according to any of claims 1-12, the method comprising the steps of:
(1) firstly, synthesizing several carbazole derivatives with special functional groups,
(2) then in the mixed solution of good solvent and poor solvent, several organic fluorescence sensing materials are obtained by self-assembly,
(3) and respectively coating the assembled several fluorescent materials on different positions of the inner side of the same glass tube to obtain the sensing array.
14. The preparation method according to claim 13, wherein when preparing the carbazole derivative of formula (I) wherein n-3, the step (1) specifically comprises:
(1a) reacting the compound shown in the formula (II) with RX' to obtain a compound shown in a formula (III);
Figure FDA0002287814920000051
x in formula (II) and formula (III), which are identical or different, are independently from each other selected from halogen; x 'in RX' is selected from halogen; r in formula (III) and RX' is as defined for formula (I);
(1b) a compound of formula (III) with R' B (OH)2Reacting to obtain a compound shown as a formula (IV);
Figure FDA0002287814920000052
formula (IV) and R' B (OH)2Wherein R' is as defined for formula (I); in the formula (IV), R and X are as defined in the formula (III);
(1c) reacting the compound shown in the formula (III) with bis (valeryl) diboron to obtain a compound shown in a formula (V);
Figure FDA0002287814920000053
in the formula (V), R is as defined in the formula (I);
(1d) reacting a compound represented by formula (IV) with a compound represented by formula (V) to obtain a carbazole derivative represented by formula (I), wherein n is 3; wherein the molar ratio of the compound shown in the formula (IV) to the compound shown in the formula (V) is 2.1: 1-2.5: 1;
when preparing the carbazole derivative with 3< n ≦ 40 in the formula (I), the step (1) specifically comprises:
(1a) reacting the compound shown in the formula (II) with RX' to obtain a compound shown in a formula (III);
Figure FDA0002287814920000061
x in formula (II) and formula (III), which are identical or different, are independently from each other selected from halogen; x 'in RX' is selected from halogen; r in formula (III) and RX' is as defined for formula (I);
(1a ') reacting the compound represented by the formula (II') with RX 'to obtain a compound represented by the formula (III');
Figure FDA0002287814920000062
x in formula (II ') and formula (III'), which are identical or different, are independently from one another selected from halogen; x 'in RX' is selected from halogen; r in the formulae (III ') and RX' is as defined for formula (I); m is an integer from 2 to 38;
(1b) a compound of formula (III) with R' B (OH)2Reacting to obtain a compound shown as a formula (IV);
Figure FDA0002287814920000063
formula (IV) and R' B (OH)2Wherein R' is as defined for formula (I); in the formula (IV), R and X are as defined in the formula (III);
(1c ') reacting the compound shown in the formula (III ') with bis (valeryl) diboron to obtain a compound shown in the formula (V ');
Figure FDA0002287814920000071
in the formula (V'), R is as defined in formula (I), and m is an integer of 2 to 38;
(1d ') reacting 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 3< n < 40; wherein the molar ratio of the compound shown in the formula (IV) to the compound shown in the formula (V') is 2.1: 1-2.5: 1.
15. The method according to claim 14, wherein the halogen is selected from Br or I, and the molar ratio of the compound of formula (IV) to the compound of formula (V) is 2.2: 1; the molar ratio of the compound shown in the formula (IV) to the compound shown in the formula (V') is 2.2: 1.
16. The production method according to any one of claims 13 to 15, wherein the step (2) comprises: dissolving the carbazole derivatives with different special functional groups obtained in the step (1) in a good solvent, then adding a poor solvent, standing, and allowing the carbazole derivatives shown in the formula (I) to be in a suspension of the organic fluorescent sensing material in a self-assembly mode.
17. The method of manufacturing according to claim 16, wherein: the step (2) further comprises: and standing the suspensions of the organic fluorescent sensing materials, taking out the organic fluorescent sensing material positioned at the bottom of the preparation container, putting the organic fluorescent sensing material in a poor solvent again, shaking up, dispersing and repeatedly washing to obtain the organic fluorescent sensing material.
18. The method of manufacturing according to claim 16, wherein: the step (3) comprises the following steps: and (3) sequentially injecting the suspensions of the organic fluorescent sensing materials obtained in the step (2) into the same glass tube, and recording to obtain the organic fluorescent sensing array after the solvent is volatilized to be dry.
19. The method of manufacturing according to claim 16, wherein: the volume ratio (ml: ml) of the good solvent to the poor solvent is 1: 3-1: 10.
20. The method of manufacturing according to claim 16, wherein: the good solvent is chloralkane and C2-5Esters, and the poor solvent is an alcoholic organic solvent or cycloalkane.
21. The method of claim 20, wherein: the good solvent is dichloromethane, chloroform, 1, 2-dichloroethane, ethyl acetate or methyl acetate; the poor solvent is methanol, ethanol or cyclohexane.
22. Use of the organic fluorescent sensing material of any one of claims 1 to 12, or a porous film of a special network structure formed by organic semiconductor nanowires or nanobelts assembled from the carbazole derivatives, wherein the sensing materials can be combined into a sensing array.
23. Use of a fluorescence sensing array according to any of claims 1-12 for distinguishing between solid explosive detections.
24. Use according to claim 23, characterized in that: the fluorescent sensing array combined by the organic fluorescent sensing materials capable of carrying out fluorescent detection distinguishing on several types of explosives can be used for detecting and distinguishing the trace of several types of explosives, and the trace is ng grade; when the several sensing materials are contacted with trace explosive steam, each material in the sensing array has different physicochemical properties, different forms of fluorescence changes can occur to the same explosive, and the fluorescence changes of the several materials in the several arrays to the same explosive are analyzed, wherein the changes are unique to each explosive, so that the method can be used for actually detecting and distinguishing several types of explosives.
25. The use according to claim 23 or 24, wherein said method for detection and discrimination of solid explosives comprises in particular: the obtained different sensing materials are coated in a quartz glass tube, explosives are placed in a heating gun, the steam concentration of the explosives is improved by setting different temperatures, when different explosive steam is in contact with organic fluorescence sensing materials with different substituted functional group side chains in a sensing array, the fluorescence of the different fluorescence sensing materials can be changed in different forms, the fluorescence change of several materials in several arrays to the same explosives is analyzed, and the changes are unique to each explosive, so that the purpose of detecting and distinguishing several types of explosives is achieved.
26. Use according to claim 23 or 24, characterized in that the types of explosives are selected from hexogen (RDX), trinitrotoluene (TNT), Dinitrotoluene (DNT), pentaerythritol tetranitrate (PETN), black powder (S), Ammonium Nitrate (AN) and 2, 3-dinitro-2, 3-Dimethylbutane (DMNB).
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108489953A (en) * 2018-05-10 2018-09-04 长春理工大学 A kind of preparation method of in-situ modification paper substrate nitro explosive fluorescent sensing material
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CN110746311B (en) * 2019-10-18 2022-10-21 北京华泰诺安探测技术有限公司 Nano fluorescent sensing material, fluorescent sensing film and film array thereof, preparation method and application
CN111334290B (en) * 2020-02-21 2021-06-01 中国科学院化学研究所 Fluorescent sensing material, preparation method thereof and application thereof in high-sensitivity explosive detection

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102947697A (en) * 2010-03-31 2013-02-27 丹麦技术大学 Multisensor array for detection of analytes or mixtures thereof in gas or liquid phase
CN103525404A (en) * 2013-10-12 2014-01-22 苏州大学 Fluorescent sensor array based on conjugated polymers and application thereof
CN106278996A (en) * 2016-07-19 2017-01-04 中国科学院化学研究所 To a few class explosive organic fluorescence sensing materials with high sensitivity fluorescence response and its preparation method and application

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10371688B2 (en) * 2016-02-10 2019-08-06 Rhode Island Board Of Education, State Of Rhode Island And Providence Plantations Sensing system based on a fluorophore array

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102947697A (en) * 2010-03-31 2013-02-27 丹麦技术大学 Multisensor array for detection of analytes or mixtures thereof in gas or liquid phase
CN103525404A (en) * 2013-10-12 2014-01-22 苏州大学 Fluorescent sensor array based on conjugated polymers and application thereof
CN106278996A (en) * 2016-07-19 2017-01-04 中国科学院化学研究所 To a few class explosive organic fluorescence sensing materials with high sensitivity fluorescence response and its preparation method and application

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Fluorescent Polymer Sensor Array for Detection and Discrimination of Explosives in Water;Marc D. Woodka等;《Anal. Chem.》;20101201;9917–9924 *
基于功能化纳米材料的光化学阵列传感器;陆跃翔;《化学进展》;20140525;931-938 *
荧光传感器阵列;刘渊等;《化学进展》;20121024;1915-1927 *

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