An organic fluorescent sensing array for selectively detecting sarin and its preparation method

Abstract

This invention relates to an organic fluorescent sensor array for the sensitive and selective detection of sarin using fluorescence methods, and its preparation method. The organic fluorescent sensor material is assembled with compounds of formula (B) and formula (C), which are insensitive to nerve agents, along with the compound of formula (A), to form an organic fluorescent sensor array consisting of material 1 and material 2. This improves upon the poor stability and susceptibility to interference when using compound (A) alone for sarin detection, while maintaining the sensitivity for sarin detection, thus improving the fluorescence stability and anti-interference capability of the detection.

Description

Technical Field

[0001] This invention belongs to the field of organic semiconductor materials technology, specifically relating to an organic fluorescent sensing array for the sensitive and selective detection of sarin using fluorescence methods and its preparation method. Background Technology

[0002] Organophosphate-based nerve agents are a class of highly toxic acetylcholinesterase inhibitors. Among all nerve agents, sarin (GB) has the highest volatility, reaching 22,000 mg / m³ at room temperature and pressure. 3 However, its absolute lethal dose is only 0.1 mg·min / L, making the portable, rapid, sensitive, and selective detection of sarin of great significance. Fluorescence sensing, as a detection technique with these characteristics, has been extensively explored in the detection of sarin. However, most reported methods are for detecting sarin simulants, such as diethyl chlorophosphate (DCP) and diisopropyl fluorophosphate (DFP), which do not achieve satisfactory results for detecting real sarin. Furthermore, these fluorescent sensing materials are inherently very sensitive to acids, inevitably producing false positive signals when encountering acids such as hydrochloric acid (HCl) and hydrofluoric acid (HF). Therefore, developing novel fluorescent sensors with high sensitivity and selectivity for real sarin is crucial for practical applications.

[0003] Fluorescence sensing arrays are a widely used method for distinguishing and detecting sarin. These methods combine multiple sensor elements in a specific geometric distribution, allowing for more comprehensive collection of optical parameters and improved fluorescence sensing performance. This makes them an effective method for distinguishing and detecting sarin. The principle behind fluorescence sensing arrays for distinguishing and detecting sarin is based on the different physicochemical reactions between the fluorescent molecules that make up the sensing elements and sarin and its interfering substances (sarin analogs, acids, and volatile organic molecules), producing different fluorescence response signals. These signals are then statistically analyzed to achieve the purpose of distinguishing and detecting sarin.

[0004] Currently, there are few reports on fluorescent sensing arrays capable of selectively detecting sarin, and they are quite expensive. Differential detection requires very complex analytical methods, and the detection limits are relatively high (mostly at the ppm level), which cannot meet practical needs. Therefore, achieving the differential detection of sarin using a simple sensing array remains a challenge. Summary of the Invention

[0005] One of the objectives of this invention is to provide a fluorescent sensing array assembled from several co-assembled organic fluorescent sensing materials that can perform highly sensitive and selective detection of sarin.

[0006] The second objective of this invention is to provide a method for preparing the aforementioned fluorescent sensing array.

[0007] A third objective of this invention is to provide applications of the aforementioned fluorescence sensing array.

[0008] This invention provides a fluorescent sensing array capable of highly sensitive and selective detection of sarin. This sensing array is co-assembled from several different organic fluorescent sensing materials. The materials used in this invention to assemble the sensing array are a series of organic fluorescent compounds based on fluorene and benzimidazole, as shown in formula (A), and a series of organic fluorescent compounds based on fluorene and benzimidazole, as shown in formula (B), or a series of organic fluorescent compounds based on fluorene and benzimidazole, as shown in formula (C). Several organic fluorescent semiconductor aggregates are obtained through co-assembly, and a sensing array capable of highly sensitive and selective fluorescent detection of sarin is prepared through a fabrication process. The materials used in this invention to assemble the sensing array, i.e., the aggregates of molecularly co-assembled particles, have a large specific surface area and numerous surface pores, which is beneficial for the diffusion and adsorption of sarin vapor on the aggregate surface. Due to the different physicochemical properties of the different co-assembled materials, they produce different responses to sarin and its interfering substances, allowing for fingerprint recognition of the target analyte sarin, resulting in excellent distinguishing and detection effects for sarin. Therefore, the organic fluorescence sensing array of the present invention can be used as a means for high-sensitivity and high-selectivity detection of sarin.

[0009] This invention is achieved through the following technical solution:

[0010] An organic fluorescent sensing array is composed of two co-assembled organic fluorescent compounds forming sensing materials. The first co-assembled organic fluorescent compound sensing material is obtained by co-assembling the compound shown in formula (A) and the compound shown in formula (B), and the second co-assembled organic fluorescent compound sensing material is obtained by co-assembling the compound shown in formula (A) and the compound shown in formula (C).

[0011]

[0012] in,

[0013] s is an integer selected from 3 to 6; n is an integer selected from 1 to 3;

[0014] m is an integer selected from 1 to 3;

[0015] Each R may be the same or different, and is independently selected from unsubstituted or optionally substituted by one, two or more Ra groups of the following: C 1-12 Alkyl, C 1-12 Alkoxy, C 6-14 Aryl, -C 6-14 Aryl-C 1-12 Alkyl, -C 6-14 Aryl-C 1-12 Alkoxy;

[0016] Each R1 may be the same or different, and is independently selected from unsubstituted or optionally substituted groups of one, two or more Rb, including the following groups: C 1-12 Alkoxy, C 1-12 Alkyl, C 6-14 Aryl, -C 6-14 Aryl-C 1-12 Alkyl, 5-14 heteroaryl, -5-14 heteroaryl-C 1-12 alkyl;

[0017] Each R2 is either identical or different, and is independently selected from C. 1-12 alkyl;

[0018] Each R3 may be the same or different, and is selected independently from C. 1-12 alkyl;

[0019] R4 is selected from O or S; each Ra and Rb may be the same or different, and are independently selected from halogens and C. 1-12 Alkyl, C 1-12 Alkoxy, C 6-14 Aryl, 5-14 heteroaryl.

[0020] According to embodiments of the invention, each R may be the same or different, and is independently selected from unsubstituted or optionally substituted groups of one, two or more Ra, including: C 1-10 Alkyl, C 6-14 Aryl, -C 6-14 Aryl-C 1-10 Alkyl, -C 6-14 Aryl-C 1-10 Alkoxy;

[0021] According to embodiments of the invention, each R1 may be the same or different, and is independently selected from unsubstituted or optionally substituted groups of one, two or more Rb, including the following groups: C 1-10 Alkoxy, C 1-10 alkyl;

[0022] According to embodiments of the present invention, each R2 may be the same or different, and is independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, nonyl, and decyl.

[0023] According to embodiments of the present invention, each R3 may be the same or different, and is independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, nonyl, and decyl.

[0024] According to an embodiment of the present invention, R4 is selected from O or S;

[0025] According to embodiments of the present invention, each Ra and Rb may be the same or different, and are independently selected from halogens and C. 1-10 Alkyl, C1-10 Alkyl group.

[0026] According to a preferred embodiment of the present invention, each R may be the same or different, and is independently selected from one of the following groups:

[0027]

[0028] Each R1 may be the same or different, and is independently selected from one of the following groups:

[0029]

[0030] The asterisk (*) indicates a connection point.

[0031] s is 3;

[0032] m is 1;

[0033] n is 1.

[0034] According to an embodiment of the present invention, in the organic fluorescent sensing array, the compound shown in formula (A) and the compound shown in formula (B) in the first organic fluorescent compound co-assembled sensing material are co-assembled in molar ratios of 5:1, 10:1, 20:1, 50:1, 100:1, and 500:1, and the compound shown in formula (A) and the compound shown in formula (C) in the second organic fluorescent compound co-assembled sensing material are co-assembled in molar ratios of 5:1, 10:1, 20:1, 50:1, 100:1, and 500:1.

[0035] According to an embodiment of the present invention, in the organic fluorescent sensing array, the number of the first organic fluorescent compound co-assembled sensing material and the second organic fluorescent compound co-assembled sensing material are both at least one, and when the total number of the two organic fluorescent compound co-assembled sensing materials is three or more, they are arranged sequentially.

[0036] According to an embodiment of the present invention, the first and second organic fluorescent compounds co-assembled sensing materials are organic semiconductor nanoparticles with a fluorescence quantum yield of 20-70%, for example 30%, 40%, 50% or 60%.

[0037] The present invention also provides a method for fabricating the organic fluorescent sensing array as described above, which includes the following steps:

[0038] (1) Prepare the compound shown in formula (A);

[0039] (2) Prepare the compound shown in formula (B);

[0040] (3) Prepare the compound shown in formula (C);

[0041] (4) Dissolve the compound shown in formula (A) and the compound shown in formula (B) in a good solvent, and then add a poor solvent to co-assemble the first organic fluorescent compound co-assembled sensing material; dissolve the compound shown in formula (A) and the compound shown in formula (C) in a good solvent, and then add a poor solvent to co-assemble the second organic fluorescent compound co-assembled sensing material.

[0042] (5) The two fluorescent materials obtained by co-assembly are coated on different positions of the same carrier to obtain the organic fluorescent sensing array;

[0043] The preparation of the compound shown in formula (A) in step (1) includes the following steps:

[0044] (A-1) Compound a1 reacts with a2 to give compound a3;

[0045] (A-2) Compound a4 reacts with RX to give compound a5;

[0046] (A-3) Compound a6 reacts with RX to give compound a7;

[0047] (A-4) Compound a7 reacts with dipentanoyl diborone to give compound a8;

[0048] (A-5) Compound a8 reacts with a3 to give compound a9;

[0049] (A-6) Compound a9 undergoes ring-opening desulfurization to yield compound a10;

[0050] (A-7) Compound a10 reacts with orthoformate ester to give compound a11;

[0051] (A-8) Compound a11 reacts with compound a5 to give the compound shown in formula (A);

[0052]

[0053] Where X is a halogen, and s, R, and R1 have the definitions described above;

[0054] The preparation of the compound shown in formula (B) in step (2) includes the following steps:

[0055] (B-1) Compound b1 reacts with dipentanoyl diborone to give compound b2;

[0056] (B-2) Compound b3 reacts with RX to give compound b4;

[0057] (B-3) Compound b5 reacts with XR2 to give compound b6;

[0058] (B-4) Compound b6 reacts with dipentanoyl diborone to give compound b7;

[0059] (B-5) Compound b7 reacts with b4 to give compound b8;

[0060] (B-6) Compound b8 reacts with compound b2 to give the compound shown in formula (B);

[0061]

[0062] Where X is a halogen, and m, R, and R2 have the definitions described above;

[0063] The preparation of the compound shown in formula (C) in step (3) includes the following steps:

[0064] (C-1) Compound c1 reacts with RX to give compound c2;

[0065] (C-2) Compound c3 reacts with XR3 to give compound c4;

[0066] (C-3) Compound c4 reacts with dipentanoyl diborone to give compound c5;

[0067] (C-4) Compound c5 reacts with c2 to give compound c6;

[0068] (C-5) Compound c6 reacts with dipentanoyl diborone to give compound c7;

[0069] (C-6) Compound c7 reacts with 2,7-dibromofluorenone or 2,7-dibromothionone to give the compound shown in formula (C);

[0070]

[0071] Where X is a halogen, and n, R, and R3 have the definitions described above.

[0072] According to the present invention, the carrier is a quartz tube or a glass tube.

[0073] According to the present invention, in step (A-1), the solvent for the reaction is a mixture of an organic solvent and water, such as a mixture of 1,4-dioxane and water, with a volume ratio of (5-8:1); the reaction temperature is 80-100°C; the reaction time is 4-12 hours; and the reaction is carried out under an inert gas atmosphere; the molar ratio of compounds a1 to a2 is 1:0.8-1.2, for example, 1:1.

[0074] According to the present invention, in step (A-2), the reaction is carried out in an organic solvent, such as dimethyl sulfoxide, at a temperature of -10 to 10°C, for example 2°C, for 2 to 4 hours. The reaction can be carried out under the action of an alkali, which can be sodium hydroxide, potassium hydroxide, lithium hydroxide or an aqueous solution thereof, such as an aqueous solution of 50% sodium hydroxide by mass. The molar ratio of compound a4 to RX is 1:2-8, for example 1:3.

[0075] According to the present invention, in step (A-3), the reaction is carried out in an organic solvent, such as dimethyl sulfoxide, at a temperature of -10 to 10°C, for example -8 to 8°C, for 2 to 4 hours. The reaction can be carried out under the action of an alkali, which can be sodium hydroxide, potassium hydroxide, lithium hydroxide or an aqueous solution thereof, for example, a 50% sodium hydroxide aqueous solution. The molar ratio of compound a6 to RX is 1:2-8, for example 1:3.

[0076] According to the present invention, in step (A-4), the reaction is carried out in an organic solvent, such as 1,4-dioxane, at a temperature of 80-100°C, for a time of 6-12 hours, under an inert gas atmosphere; the molar ratio of compound a7 to dipentanoyl diborone is 1:1.5-2.5, for example 1:2.

[0077] According to the present invention, in step (A-5), the solvent for the reaction is a mixture of an organic solvent and water, such as a mixture of 1,4-dioxane and water, with a volume ratio of 5:1; the reaction temperature is 80-100°C; the reaction time is 6-12 hours; and the reaction is carried out in an inert gas atmosphere; the molar ratio of compounds a3 to a8 is 1:0.8-1.2, for example, 1:1.

[0078] According to the present invention, in step (A-6), the reaction is carried out in a mixed solvent of two organic solvents, such as a mixed solution of tetrahydrofuran and ethanol, in a volume ratio of 1:1; the reaction can be carried out in the presence of a reducing agent, which can be sodium borohydride, potassium borohydride, sodium borohydride acetate, or sodium cyanoborohydride; the reaction can be carried out in the presence of a catalyst, which can be cobalt chloride hexahydrate; the molar ratio of compound a9, reducing agent, and catalyst can be 1:1-10:0.01-0.5, for example, 1:2:0.2; the reaction temperature is 60-80°C, and the reaction time is 1-4 hours.

[0079] According to the present invention, in step (A-7), the reaction is carried out in a mixed solvent of two organic solvents, such as a mixed solution of tetrahydrofuran and methanol, with a volume ratio of 1:1; the reaction can be carried out in the presence of a catalyst, which can be aminosulfonic acid; the orthoformate can be trimethyl orthoformate, triethyl orthoformate, or triisopropyl orthoformate; the molar ratio of compound a10, orthoformate, and catalyst can be 1:1-10:0.01-0.5, for example, 1:2:0.2; the reaction temperature is 60-80°C, and the reaction time is 1-3 hours.

[0080] According to the present invention, in step (A-8), the solvent for the reaction is a mixture of an organic solvent and water, such as a mixture of toluene and water, with a volume ratio of 5:1; the reaction temperature is 80–110°C, for example 95°C; the reaction time is 12–36 hours; the reaction is carried out in an inert gas atmosphere; and the molar ratio of compound a5 to compound a11 is 1:0.3–0.7, for example 1:0.5.

[0081] According to the present invention, in steps (A-1), (A-5), and (A-8), the reaction is carried out in a catalyst system comprising a palladium catalyst and an alkali metal salt; the palladium catalyst is tetrakis(triphenylphosphine)palladium; the alkali metal salt is potassium acetate, sodium carbonate, potassium carbonate, or cesium carbonate; relative to 1 equivalent of the starting compound, the amount of palladium catalyst added is 5 to 20% equivalent, and the amount of alkali metal salt added is 1 to 5 equivalents.

[0082] According to the present invention, in step (A-4), the reaction is carried out in a catalyst system comprising a palladium catalyst and an alkali metal salt; the palladium catalyst is [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride; the alkali metal salt is at least one selected from potassium acetate, sodium carbonate, potassium carbonate, and cesium carbonate; the amount of palladium catalyst added is 5 to 20% equivalent relative to 1 equivalent of the starting compound, and the amount of alkali metal salt added is 1 to 5 equivalents.

[0083] According to the present invention, in step (B-1), the reaction is carried out in an organic solvent, such as 1,4-dioxane, at a temperature of 80-100°C for 6-12 hours, and under an inert gas atmosphere; the molar ratio of compound b1 to dipentanoyl diborone is 1:1.5-2.5, for example 1:2.

[0084] According to the present invention, in step (B-2), the reaction is carried out in an organic solvent, such as dimethyl sulfoxide, at a temperature of -10 to 10°C, for example 2°C, for 2 to 4 hours. The reaction can be carried out under the action of an alkali, which can be sodium hydroxide, potassium hydroxide, lithium hydroxide or an aqueous solution thereof, such as an aqueous solution of 50% sodium hydroxide by mass. The molar ratio of compound b3 to RX is 1:2-8, for example 1:3.

[0085] According to the present invention, in step (B-3), the reaction is carried out in an organic solvent, such as tetrahydrofuran, at a temperature of 30-50°C, for example 30°C, for a reaction time of 2-5 hours, and the reaction is carried out under the action of an organic base, such as potassium tert-butoxide; the molar ratio of compound b5 to XR2 is 1:1-3, for example 1:1.5.

[0086] According to the present invention, in step (B-4), the reaction is carried out in an organic solvent, such as 1,4-dioxane, at a temperature of 80-100°C for 6-12 hours, and under an inert gas atmosphere; the molar ratio of compound b6 to dipentanoyl diborone is 1:1-2, for example 1:1.5.

[0087] According to the present invention, in step (B-5), the solvent for the reaction is a mixture of an organic solvent and water, such as toluene or a mixture of 1,4-dioxane and water, with a volume ratio of 5:1; the reaction temperature is 80–100°C; the reaction time is 8–12 hours; and the reaction is carried out in an inert gas atmosphere. The molar ratio of compounds b4 to b7 is 1:0.8–1.2, for example, 1:1.

[0088] According to the present invention, in step (B-6), the solvent for the reaction is a mixture of an organic solvent and water, such as a mixture of toluene and water, with a volume ratio of 5:1; the reaction temperature is 80-110°C, for example 95°C; the reaction time is 12-36 hours; the reaction is carried out in an inert gas atmosphere; and the molar ratio of compound b2 to compound b8 is 1:0.3-0.7, for example 1:0.5.

[0089] According to the present invention, in steps (B-1) and (B-4), the reaction is carried out in a catalyst system, the catalyst system comprising a palladium catalyst and an alkali metal salt; the palladium catalyst is [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride; the alkali metal salt is potassium acetate, sodium carbonate, potassium carbonate, or cesium carbonate; relative to 1 equivalent of the raw material compound, the amount of palladium catalyst added is 5 to 20% equivalent, and the amount of alkali metal salt added is 1 to 5 equivalents.

[0090] According to the present invention, in steps (B-5) and (B-6), the reaction is carried out in a catalyst system, the catalyst system comprising a palladium catalyst and an alkali metal salt; the palladium catalyst is tetrakis(triphenylphosphine)palladium; the alkali metal salt is potassium acetate, sodium carbonate, potassium carbonate, or cesium carbonate; relative to 1 equivalent of the raw material compound, the amount of palladium catalyst added is 5 to 20% equivalent, and the amount of alkali metal salt added is 1 to 5 equivalents.

[0091] According to the present invention, in step (C-1), the reaction is carried out in an organic solvent, such as dimethyl sulfoxide, at a temperature of -10 to 10°C, for example 2°C, for 2 to 4 hours. The reaction can be carried out under the action of an alkali, which can be sodium hydroxide, potassium hydroxide, lithium hydroxide or an aqueous solution thereof, for example, an aqueous solution of 50% sodium hydroxide by mass. The molar ratio of compound c1 to RX is 1:2-8, for example 1:3.

[0092] According to the present invention, in step (C-2), the reaction is carried out in an organic solvent, such as tetrahydrofuran, at a temperature of 30-50°C, for example 40°C, for a reaction time of 2-5 hours, and the reaction is carried out under the action of an organic base, such as potassium tert-butoxide; the molar ratio of compound c3 to XR3 is 1:1-3, for example 1:1.5.

[0093] According to the present invention, in step (C-3), the reaction is carried out in an organic solvent, such as 1,4-dioxane, at a temperature of 80-100°C for 6-12 hours, and under an inert gas atmosphere; the molar ratio of compound C4 to dipentanoyl diborone is 1:1-2, for example, 1:1.5.

[0094] According to the present invention, in step (C-4), the solvent for the reaction is a mixture of an organic solvent and water, such as toluene or a mixture of 1,4-dioxane and water, with a volume ratio of 5:1; the reaction temperature is 80–100°C; the reaction time is 8–12 hours; and the reaction is carried out in an inert gas atmosphere. The molar ratio of compounds c2 to c5 is 1:0.8–1.2, for example, 1:1.

[0095] According to the present invention, in step (C-5), the reaction is carried out in an organic solvent, such as 1,4-dioxane, at a temperature of 80-100°C for 6-12 hours, and under an inert gas atmosphere; the molar ratio of compound C4 to dipentanoyl diborone is 1:1-2, for example, 1:1.5.

[0096] According to the present invention, in step (C-6), the solvent for the reaction is a mixture of an organic solvent and water, such as toluene or a mixture of 1,4-dioxane and water, in a volume ratio of 5:1; the reaction temperature is 80–110°C, for example 95°C; the reaction time is 12–36 hours; the reaction is carried out in an inert gas atmosphere; and the molar ratio of 2,7-dibromofluorenone or 2,7-dibromothionone to compound C7 is 1:0.3–0.7, for example 1:0.5.

[0097] According to the present invention, in steps (C-3) and (C-5), the reaction is carried out in a catalyst system, the catalyst system comprising a palladium catalyst and an alkali metal salt; the palladium catalyst is [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride; the alkali metal salt is potassium acetate, sodium carbonate, potassium carbonate, or cesium carbonate; relative to 1 equivalent of the raw material compound, the amount of palladium catalyst added is 5 to 20% equivalent, and the amount of alkali metal salt added is 1 to 5 equivalents.

[0098] According to the present invention, in steps (C-4) and (C-6), the reaction is carried out in a catalyst system, the catalyst system comprising a palladium catalyst and an alkali metal salt; the palladium catalyst is tetrakis(triphenylphosphine)palladium; the alkali metal salt is potassium acetate, sodium carbonate, potassium carbonate, or cesium carbonate; relative to 1 equivalent of the raw material compound, the amount of palladium catalyst added is 5 to 20% equivalent, and the amount of alkali metal salt added is 1 to 5 equivalents.

[0099] According to an embodiment of the present invention, the molar ratio of compound (A) and compound (B) in step (4) can be (1-2000):1, for example (1-500):1, with examples being 1:1, 5:1, 10:1, 50:1, 100:1, and 500:1; the molar ratio of compound (A) and compound (C) can be (1-2000):1, for example (1-500):1, with examples being 1:1, 5:1, 10:1, 50:1, 100:1, and 500:1.

[0100] According to the present invention, the volume ratio (ml:ml) of the good solvent to the bad solvent in step (4) is 1:5 to 1:50, preferably 1:10.

[0101] According to the present invention, the good solvent in step (4) is a haloalkane solvent, for example, at least one selected from dichloromethane, chloroform, 1,2-dichloroethane or 1,4-dichlorobutane.

[0102] According to the present invention, the undesirable solvent in step (4) is an alkane solvent, for example, it may be selected from at least one of cyclohexane or n-hexane.

[0103] According to the present invention, step (5) includes: sequentially injecting the suspensions of the first and second organic fluorescent sensing materials obtained in step (4) into different positions of the same carrier, and waiting for the solvent to evaporate to dryness to obtain the organic fluorescent sensing array.

[0104] The co-assembled material of compound (A) and compound (B) of the present invention has an amorphous small particle morphology, and the co-assembled material of compound (A) and compound (C) also has an amorphous small particle morphology. These materials have a large specific surface area and different fluorescence responses to sarin and its interfering substances. Based on the fluorescence response analysis, sarin can be distinguished and detected.

[0105] The present invention also provides the application of the fluorescence sensing array described above in distinguishing between sarin and interfering gases.

[0106] According to the present invention, the fluorescence sensing array is composed of two co-assembled organic fluorescence sensing materials, and the fluorescence sensing array can perform rapid, high-sensitivity, and high-selectivity fluorescence differentiation detection of gaseous sarin.

[0107] According to the present invention, two co-assembled sensing materials are spin-coated onto a carrier. When sarin and interfering gas vapors (sarin simulant, volatile acid, volatile small organic molecules) come into contact with co-assembled organic fluorescent sensing materials doped with different acceptors, the fluorescence of the different fluorescent sensing materials will change in different forms. By analyzing the fluorescence change signals, the purpose of distinguishing and detecting sarin can be achieved. In the fluorescent sensing array of the present invention, the fluorescence response of material 1 is named R1, and the fluorescence response of material 2 is named R2. In this way, the different forms of fluorescence changes obtained by the fluorescent sensing array are different for sarin and interfering gas, and this change is unique to sarin (the fluorescence change signal of sarin is an irreversibly enhanced signal response, while the fluorescence change signal of interfering gas is a recoverable response). Therefore, this sensing array composed of two different organic fluorescent sensing co-assembled materials can quickly detect and distinguish sarin using fluorescence.

[0108] According to the present invention, the sarin, also known as sarin poison, is chemically named isopropyl methylphosphonate, and its English name is Sarin. It belongs to Class G nerve agents and can paralyze the central nervous system.

[0109] Preferably, the sarin analogue is selected from at least one of diethyl chlorophosphate (DCP), diisopropyl fluorophosphate (DFP), and diethyl cyanophosphate (DCNP); the acid is selected from at least one of hydrochloric acid (HCl), hydrofluoric acid (HF), and acetic acid (HAc); and the volatile organic small molecules include volatile benzene compounds, ammonia, alkanes, chloroalkanes, ethers, alcohols, etc., such as toluene, ammonia, n-hexane, dichloromethane, diethyl ether, methanol, etc.

[0110] According to an embodiment of the present invention, the detected sarin concentration range is above 50 ppb, for example, 50 ppb-3000 ppm.

[0111] A portable device for rapid detection and differentiation of sarin includes an organic fluorescent sensor array as described above.

[0112] Beneficial effects

[0113] 1. The co-assembled organic fluorescent sensor array material of the present invention is a film composed of small particles of amorphous organic semiconductor material, which has a large specific surface area, can effectively detect sarin, has high sensitivity, can be used for trace detection, and has a detection limit as low as 50 ppb.

[0114] 2. The organic fluorescent sensing material of the present invention is formed by co-assembling the compound shown in formula (B) and the compound shown in formula (C) with the compound shown in formula (A) to form an organic fluorescent sensing array composed of material 1 and material 2, which improves the shortcomings of poor stability and susceptibility to interference when using compound (A) alone to detect sarin. While maintaining the sensitivity to sarin detection, it improves the fluorescence stability and anti-interference ability of the detection.

[0115] 3. The fluorescence response results R1 and R2 of materials 1 and 2 in the organic fluorescence sensing array of the present invention can be analyzed and processed to effectively screen out sarin from the interfering substances, thereby enabling high-sensitivity and high-selectivity differentiation and detection of the target analyte sarin.

[0116] 4. The organic fluorescence sensor array described in this invention has a simple structure and is easy to operate. Through design, this organic fluorescence sensor array can be made into a small to medium-sized portable device for rapid sarin detection, which is convenient for application and service to society. This invention is of great significance and has great development and application prospects.

[0117] 5. The present invention also provides a method for preparing two co-assembled organic fluorescent sensing materials in the organic fluorescent sensing array. The preparation method is simple and facilitates the large-scale production of organic fluorescent sensing arrays.

[0118] Terminology Definitions and Explanations

[0119] The term "halogen" refers to F, Cl, Br, and I. In other words, F, Cl, Br, and I can be described as "halogens" in this specification.

[0120] Term "C" 1-12 "alkyl" should be understood to refer to a straight-chain or branched saturated monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably C12. 1-10 Alkyl group. "C" 1-10"alkyl" should be understood to preferably represent a straight-chain or branched saturated monovalent hydrocarbon group having 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms. The alkyl group is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl, or 1,2-dimethylbutyl, etc., or isomers thereof. In particular, the group has 1, 2, 3, 4, 5, or 6 carbon atoms ("C"). 1-6 Alkyl groups, such as methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, and more particularly, the groups having 1, 2, or 3 carbon atoms (“C”). 1-3 Alkyl), such as methyl, ethyl, n-propyl or isopropyl.

[0121] Term "C" 6-14 "Aryl" should be understood as representing a monovalent aromatic or partially aromatic monocyclic, bicyclic, or tricyclic hydrocarbon ring ("C") having 6, 7, 8, 9, 10, 11, 12, 13, or 14 carbon atoms. 6-14 Aryl), particularly a ring with 6 carbon atoms (“C6 aryl”), such as phenyl; or biphenyl, or a ring with 9 carbon atoms (“C9 aryl”), such as indenyl or indenyl, or a ring with 10 carbon atoms (“C9 aryl”). 10 Aryl groups, such as tetrahydronaphthyl, dihydronaphthyl, or naphthyl, or rings with 13 carbon atoms (“C”). 13 Aryl groups, such as fluorene groups, or rings with 14 carbon atoms (“C”). 14 Aryl), for example, anthracene.

[0122] The term "5-14 cyclic heteroaryl" should be understood to include monovalent monocyclic, bicyclic, or tricyclic aromatic ring systems having 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14 ring atoms, particularly 5, 6, 9, or 10 carbon atoms, and containing 1 to 5, preferably 1 to 3, heteroatoms independently selected from N, O, and S, and in each case may be benzofused. Specifically, the heteroaryl group is selected from thienyl, furanyl, pyrroleyl, oxazolyl, thiazolyl, imidazoleyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, thia-4H-pyrazolyl, and their benzo[derivatives], such as benzofuranyl, benzothienyl, benzooxazolyl, benzoisooxazolyl, benzoimidazolyl, benzotriazolyl, indazole, indolyl, isindolyl, etc.; or pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, and their benzo[derivatives], such as quinolinyl, quinazolinyl, isoquinolinyl, etc.; or acrylinyl, inazinyl, purinyl, and their benzo[derivatives]; or terpenolyl, phthalazinyl, quinazolinyl, quinoxolinyl, naphridinyl, pteridinyl, carbazolyl, acridineyl, phenazinyl, phenothiazinyl, phenothiazinyl, etc.

[0123] The above refers to the term "C" 1-12 The definition of "alkyl" also applies to compounds containing "C". 1-12 Other terms for "alkyl", such as the term "C 1-20 Alkoxy, C 6-14 Aryl-C 1-12 Alkyl groups, etc. Similarly, "C" 6-14 The same definition is used for "aryl" and other terms throughout the text. Attached Figure Description

[0124] Figure 1 NMR data spectrum of compound A1 in Example 1.

[0125] Figure 2 NMR data spectrum of compound B1 in Example 2.

[0126] Figure 3 NMR data spectrum of compound C1 in Example 3.

[0127] Figure 4 The SEM image of the organic fluorescent sensing material constructed by co-assembling compounds A1 and B1 in a molar ratio of 20:1 in Example 4 shows that it has an amorphous small particle network porous structure.

[0128] Figure 5 The SEM image of the organic fluorescent sensing material constructed by co-assembling compounds A1 and C1 in a molar ratio of 50:1 in Example 5 shows that it has an amorphous small particle network porous structure.

[0129] Figure 6 The absorption fluorescence spectra of compounds A1 and B1 in this invention show that the fluorescence spectrum of compound A1 partially overlaps with the absorption spectrum of compound B1, indicating that fluorescence energy resonance transfer occurs between the two (the solid line and the dashed line are the absorption fluorescence spectra of compound A1 and compound B1, respectively).

[0130] Figure 7 The absorption fluorescence spectra of compounds A1 and C1 in this invention show that the fluorescence spectrum of compound A1 partially overlaps with the absorption spectrum of compound C1, indicating that fluorescence energy resonance transfer occurs between the two (the solid line and the dashed line are the absorption fluorescence spectra of compound A1 and compound C1, respectively).

[0131] Figure 8 The real-time fluorescence detection curves of sarin by an organic fluorescence sensing array consisting of organic fluorescent sensing material 1, constructed by co-assembling compounds A1 and B1 in a molar ratio of 20:1 in Example 4, and organic fluorescent sensing material 2, constructed by co-assembling compounds A1 and C1 in a molar ratio of 50:1 in Example 5 of this invention.

[0132] Figure 9 The real-time fluorescence detection curves of DCP formed by the organic fluorescent sensing material 1 constructed by co-assembling compounds A1 and B1 in a molar ratio of 20:1 in Example 4 and the organic fluorescent sensing material 2 constructed by co-assembling compounds A1 and C1 in a molar ratio of 50:1 in Example 5 of this invention.

[0133] Figure 10 The real-time fluorescence detection curves of HCl by an organic fluorescent sensing array composed of organic fluorescent sensing material 1, constructed by co-assembling compounds A1 and B1 in a molar ratio of 20:1 in Example 4, and organic fluorescent sensing material 2, constructed by co-assembling compounds A1 and C1 in a molar ratio of 50:1 in Example 5 of this invention.

[0134] Figure 11 The real-time fluorescence detection curves of HF by an organic fluorescent sensing array composed of organic fluorescent sensing material 1, constructed by co-assembling compounds A1 and B1 in a molar ratio of 20:1 in Example 4, and organic fluorescent sensing material 2, constructed by co-assembling compounds A1 and C1 in a molar ratio of 50:1 in Example 5 of this invention.

[0135] Figure 12The real-time fluorescence detection curves of n-hexane by an organic fluorescent sensing array consisting of organic fluorescent sensing material 1, constructed by co-assembling compounds A1 and B1 in a molar ratio of 20:1 in Example 4, and organic fluorescent sensing material 2, constructed by co-assembling compounds A1 and C1 in a molar ratio of 50:1 in Example 5 of this invention.

[0136] Figure 13 The real-time fluorescence detection curves of toluene by an organic fluorescence sensing array consisting of organic fluorescent sensing material 1, constructed by co-assembling compounds A1 and B1 in a molar ratio of 20:1 in Example 4, and organic fluorescent sensing material 2, constructed by co-assembling compounds A1 and C1 in a molar ratio of 50:1 in Example 5 of this invention.

[0137] Figure 14 The real-time fluorescence detection curves of methanol by an organic fluorescent sensing array consisting of organic fluorescent sensing material 1, constructed by co-assembling compounds A1 and B1 in a molar ratio of 20:1 in Example 4, and organic fluorescent sensing material 2, constructed by co-assembling compounds A1 and C1 in a molar ratio of 50:1 in Example 5 of this invention.

[0138] Figure 15 The real-time fluorescence detection curves of chloroform by an organic fluorescent sensing array composed of organic fluorescent sensing material 1, constructed by co-assembling compounds A1 and B1 in a molar ratio of 20:1 in Example 4, and organic fluorescent sensing material 2, constructed by co-assembling compounds A1 and C1 in a molar ratio of 50:1 in Example 5 of this invention.

[0139] Figure 16 The real-time fluorescence detection curves of tetrahydrofuran for an organic fluorescent sensing array composed of organic fluorescent sensing material 1, constructed by co-assembling compounds A1 and B1 in a molar ratio of 20:1 in Example 4, and organic fluorescent sensing material 2, constructed by co-assembling compounds A1 and C1 in a molar ratio of 50:1 in Example 5 of this invention.

[0140] Figure 17 The real-time fluorescence detection curves of ethyl acetate by an organic fluorescence sensing array composed of organic fluorescent sensing material 1, constructed by co-assembling compounds A1 and B1 in a molar ratio of 20:1 in Example 4, and organic fluorescent sensing material 2, constructed by co-assembling compounds A1 and C1 in a molar ratio of 50:1 in Example 5 of this invention.

[0141] Figure 18The real-time fluorescence detection curves of acetone by an organic fluorescent sensing array consisting of organic fluorescent sensing material 1, constructed by co-assembling compounds A1 and B1 in a molar ratio of 20:1 in Example 4, and organic fluorescent sensing material 2, constructed by co-assembling compounds A1 and C1 in a molar ratio of 50:1 in Example 5 of this invention.

[0142] Figure 19 In Example 4, the fluorescence response of the organic fluorescent sensing material 1, constructed by co-assembling compounds A1 and B1 in a molar ratio of 20:1, to sarin and the aforementioned interfering substances is denoted as R1. The absolute value of the fluorescence response of the organic fluorescent sensing material 1, constructed by co-assembling compounds A1 and B1 in a molar ratio of 20:1, to sarin and the aforementioned interfering substances is denoted as |R1|. In Example 5, the fluorescence response of the organic fluorescent sensing material 2, constructed by co-assembling compounds A1 and C1 in a molar ratio of 50:1, to sarin and the aforementioned interfering substances is denoted as R2. The absolute value of the fluorescence response of the organic fluorescent sensing material 2, constructed by co-assembling compounds A1 and C1 in a molar ratio of 50:1, to sarin and the aforementioned interfering substances is denoted as |R2|. A graph is plotted based on R1 / |R2| and R2 / |R1|. Detailed Implementation

[0143] The technical solution of the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following embodiments are merely illustrative and explanatory of the present invention, and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.

[0144] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.

[0145] Example 1

[0146] Compound A1 was prepared by the following method:

[0147]

[0148] (1) Dissolve 10 g of 2,7-dibromofluorene and 11.5 g of bromohexane in 40 mL of dimethyl sulfoxide (DMSO) solution, slowly add 10 mL of 50% sodium hydroxide aqueous solution, react at room temperature for 3 h, add 100 mL of water to quench the reaction, then extract with ethyl acetate three times, and finally obtain the product (TM-1) by column chromatography.

[0149] (2) Take 5 g of the product obtained in step (1) and add it to 40 mL of 1,4-dioxane solution. Then add 3 equivalents of dipentanoyl diborone, 8 equivalents of potassium acetate, and 10% equivalents of [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride. After reacting for 6 hours under argon protection at 80 °C, the product (TM-2) is obtained by column chromatography.

[0150] (3) Take 3.6 g of isobutoxyphenylboronic acid and 4.12 g of dibromobenzothiadiazole, add them to a mixture of 30 mL of 1,4-dioxane solution and 5 mL of water, add 10% equivalent of tetra(triphenylphosphine)palladium and 3 equivalents of cesium carbonate, and react for 6 hours under argon protection at 80 °C. The product (TM-3) is obtained by column chromatography.

[0151] (4) Take 2 g of the product obtained in step (3) and add it to 40 mL of 1,4-dioxane solution. Add 1.5 equivalents of dipentanoyl diborone, 4 equivalents of potassium acetate, and 10% equivalents of [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride. After reacting for 6 hours under argon protection at 80 °C, the product (TM-4) is obtained by column chromatography.

[0152] (5) Take 1 mmol of the product from steps (1) and (4) respectively and add it to a mixture of 30 mL of 1,4-dioxane solution and 5 mL of water. Add 10% equivalent of tetra(triphenylphosphine)palladium and 3 equivalents of cesium carbonate. After reacting for 6 hours under argon protection at 80 °C, the product (TM-5) is obtained by column chromatography.

[0153] (6) Take 1.35 g of the product obtained in step (5) and add it to a mixed solution of 10 mL tetrahydrofuran and 10 mL ethanol. Then add 5 equivalents of sodium borohydride and 5% cobalt chloride hexahydrate. After refluxing for 2 h, the product (TM-6) is obtained by column chromatography.

[0154] (7) Take 0.67 g of the product obtained in step (6) and add it to a mixture of 5 mL tetrahydrofuran and 5 mL methanol. Then add 2 equivalents of triethyl orthoformate and 5% aminosulfonic acid. After reacting for 2 h, the product (TM-7) is obtained by column chromatography.

[0155] (8) Take 0.4 mmol and 0.8 mmol of the products from steps (2) and (7) respectively, and add them to a mixture of 20 mL of toluene solution and 4 mL of water. Add 10% equivalent of tetra(triphenylphosphine)palladium and 5 equivalents of potassium carbonate. After reacting overnight under argon protection at 95 °C, compound A1 is obtained by column chromatography. Its NMR data is shown in the figure below. Figure 1 As shown.

[0156] Example 2

[0157] The following method is used to prepare compound B1:

[0158]

[0159] (1) 2 g of 4,7-dibromobenzothiadiazole was added to 40 mL of 1,4-dioxane solution, and 3 equivalents of dipentanoyl diborone, 5 equivalents of potassium acetate, and 10% equivalents of [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride were added. After reacting for 6 hours under argon protection at 80 °C, the product (TN-1) was obtained by column chromatography.

[0160] (2) Dissolve 10 g of 2,7-dibromofluorene and 6 g of bromoethane in 40 mL of dimethyl sulfoxide (DMSO) solution, slowly add 10 mL of 50% sodium hydroxide aqueous solution, react at room temperature for 3 h, add 100 mL of water to quench the reaction, then extract with ethyl acetate three times, and finally obtain the product (TN-2) by column chromatography.

[0161] (3) Add 5 g of 2-(4-bromophenyl)benzimidazole to 30 mL of tetrahydrofuran solution, add 10% potassium tert-butoxide and 3 equivalents of iodomethane, react at 30 °C for 3 hours, then extract three times with ethyl acetate, and finally obtain the product (TN-3) by column chromatography.

[0162] (4) Take 4 g of the product obtained in step (3) and add it to 40 mL of 1,4-dioxane solution. Add 1.5 equivalents of dipentanoyl diborone, 3 equivalents of potassium acetate, and 10% equivalents of [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride. After reacting for 6 hours under argon protection at 80 °C, the product (TN-4) is obtained by column chromatography.

[0163] (5) Take 4 g of the product from step (2) and 3 g of the product from step (4) and add them to a mixture of 20 mL of 1,4-dioxane solution and 4 mL of water. Add 10% equivalent of tetra(triphenylphosphine)palladium and 3 equivalents of potassium carbonate. React for 12 hours under argon protection at 95 °C. Obtain the product (TN-5) by column chromatography.

[0164] (6) Take 2 g of the product from step (5) and 0.8 g of the product from step (1) and add them to a mixture of 20 mL of toluene solution and 4 mL of water. Add 10% equivalent of tetra(triphenylphosphine)palladium and 3 equivalents of potassium carbonate. React at 95 °C under argon protection for 12 hours. Obtain compound B1 by column chromatography. Its NMR data is shown below. Figure 2 As shown.

[0165] Example 3

[0166] The following method is used to prepare compound C1:

[0167]

[0168] (1) Dissolve 10 g of 2,7-dibromofluorene and 7 g of bromobutane in 40 mL of dimethyl sulfoxide (DMSO) solution, slowly add 10 mL of 50% sodium hydroxide aqueous solution, react at room temperature for 3 h, add 100 mL of water to quench the reaction, then extract with ethyl acetate three times, and finally obtain the product (TD-1) by column chromatography.

[0169] (2) Add 5 g of 2-(4-bromophenyl)benzimidazole to 30 mL of tetrahydrofuran solution, add 10% potassium tert-butoxide and 3 equivalents of iodomethane, react at 30 °C for 3 hours, then extract three times with ethyl acetate, and finally obtain the product (TD-2) by column chromatography.

[0170] (3) Take 4 g of the product obtained in step (2) and add it to 40 mL of 1,4-dioxane solution. Add 1.5 equivalents of dipentanoyl diborone, 3 equivalents of potassium acetate, and 10% equivalents of [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride. After reacting for 6 hours under argon protection at 80 °C, the product (TD-3) is obtained by column chromatography.

[0171] (4) Take 4 g of the product from step (1) and 3 g of the product from step (3) and add them to a mixture of 20 mL of 1,4-dioxane solution and 4 mL of water. Add 10% equivalent of tetra(triphenylphosphine)palladium and 3 equivalents of potassium carbonate. Under argon protection at 95 °C, react for 12 hours and obtain the product (TD-4) by column chromatography.

[0172] (5) Take 3 g of the product obtained in step (4) and add it to 40 mL of 1,4-dioxane solution. Add 1.5 equivalents of dipentanoyl diborone, 3 equivalents of potassium acetate, and 10% equivalents of [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride. After reacting for 6 hours under argon protection at 80 °C, the product (TD-5) is obtained by column chromatography.

[0173] (6) Take 3 grams of the product from step (5) and add it to a mixture of 20 mL of 1,4-dioxane solution and 4 mL of water. Add 0.5 equivalents of 2,7-dibromofluorenone, 10 equivalents of tetra(triphenylphosphine)palladium, and 3 equivalents of potassium carbonate. Under argon protection at 95°C, react for 12 hours. The compound C1 is obtained by column chromatography. Its NMR data is shown below. Figure 3 As shown.

[0174] Example 4

[0175] Compounds A1 and B1 were dissolved in chloroform (a good solvent) to obtain solutions with a concentration of 5 mg / mL. Then, compounds A1 and B1 were mixed together at molar ratios of 5:1, 10:1, 20:1, 50:1, 100:1, and 500:1, and then assembled using n-hexane (a poor solvent). The volume ratio of good solvent to poor solvent was 1:10. After standing for 72 hours, a suspension of organic fluorescent sensing co-assembled material 1 was obtained.

[0176] Example 5

[0177] Compounds A1 and C1 were dissolved in chloroform, a good solvent, to obtain solutions with a concentration of 5 mg / mL. Then, compounds A1 and C1 were mixed together at molar ratios of 10:1, 20:1, 50:1, 100:1, and 500:1, respectively, and then co-assembled with n-hexane, a poor solvent, with a volume ratio of good solvent to poor solvent of 1:10. After standing for 72 hours, a suspension of organic fluorescent sensing co-assembled material 2 was obtained.

[0178] Example 6

[0179] The suspensions prepared in Examples 4 and 5 were pipetted to remove samples from the bottom of the containers and placed on a clean silicon wafer. After the solutions had completely evaporated, they were placed in an ion sputtering machine (Leica) and evacuated to a vacuum level of 10. -5 After p, surface sputtering of platinum particles began for 120 s. The silicon wafer was then removed and placed under a scanning electron microscope (Hitachi S4800) to observe its morphology. (EM image follows) Figure 4 and 5 This indicates that the material has a porous structure composed of amorphous small particles, which provides sufficient specific surface area for fluorescence sensing performance.

[0180] Example 7

[0181] The solids from the suspensions obtained in Examples 4 and 5 were taken from the bottom of the container and coated successively at different locations inside the same quartz tube to prepare a fluorescent sensing array containing two materials. The quartz tube was connected to a micro-flow pump at a pumping speed of 150 mL / min. The porous membrane coated inside the quartz tube was excited using a 385 nm excitation light source. Sarin vapor was diluted with 40 mL glass bottles to obtain concentrations of 50 ppb, 200 ppb, and 500 ppb. The sarin was pumped to the material surface using the flow pump. The test results showed that at the above three concentrations, both Material 1 and Material 2 exhibited the following characteristics: Figure 8 The irreversible enhancement of fluorescence is shown.

[0182] Example 8

[0183] Using the same method as in Example 7, except that the analyte was replaced with DCP at concentrations of 50 ppb, 200 ppb, and 500 ppb, the detection results at the above three concentrations showed the following... Figure 9 The fluorescence changes are shown.

[0184] Example 9

[0185] Using the same method as in Example 7, except that the analyte was replaced with 10 ppm, 20 ppm, and 40 ppm HCl, the detection results at the above three concentrations appeared as follows: Figure 10 The fluorescence changes are shown.

[0186] Example 10

[0187] Using the same method as in Example 7, except that the analyte was replaced with HF at concentrations of 10 ppm, 20 ppm, and 40 ppm, the detection results at the above three concentrations showed the following... Figure 11 The fluorescence changes are shown.

[0188] Example 11

[0189] Using the same method as in Example 7, except that the analyte was replaced with 40 ppm, 160 ppm, and 400 ppm of n-hexane, the detection results at the above three concentrations showed the following... Figure 12 The fluorescence changes are shown.

[0190] Example 12

[0191] Using the same method as in Example 7, except that the analyte was replaced with toluene at concentrations of 30 ppm, 120 ppm, and 300 ppm, the detection results at the above three concentrations showed the following... Figure 13 The fluorescence changes are shown.

[0192] Example 13

[0193] Using the same method as in Example 7, except that the analyte was replaced with methanol at concentrations of 65 ppm, 260 ppm, and 650 ppm, the detection results at the above three concentrations showed the following... Figure 14 The fluorescence changes are shown.

[0194] Example 14

[0195] Using the same method as in Example 7, except that the analyte was replaced with chloroform at concentrations of 50 ppm, 200 ppm, and 500 ppm, the detection results at the above three concentrations showed the following... Figure 15 The fluorescence changes are shown.

[0196] Example 15

[0197] Using the same method as in Example 7, except that the analyte was replaced with tetrahydrofuran at concentrations of 50 ppm, 200 ppm, and 500 ppm, the detection results at the above three concentrations showed the following... Figure 16 The fluorescence changes are shown.

[0198] Example 16

[0199] Using the same method as in Example 7, except that the analyte was replaced with ethyl acetate at concentrations of 50 ppm, 200 ppm, and 500 ppm, the detection results at the above three concentrations showed the following... Figure 17 The fluorescence changes are shown.

[0200] Example 17

[0201] Using the same method as in Example 7, except that the analyte was replaced with acetone at concentrations of 60 ppm, 240 ppm, and 600 ppm, the detection results at the above three concentrations showed the following... Figure 18 The fluorescence changes are shown.

[0202] Example 18

[0203] The fluorescence response changes of sarin were graphically analyzed using a sensor array composed of two organic fluorescent materials (material 1 and material 2) assembled in Examples 4 and 5. The fluorescence response of material 1 was named R1, and its absolute value was named |R1|. The fluorescence response of material 2 was named R2, and its absolute value was named |R2|. Based on the ratios of R1 / |R2| and R2 / |R1|, the fluorescence response changes of the sensor array to sarin were unique. Figure 19 As shown (the fluorescence change signal of sarin is an irreversibly enhanced signal response, while the fluorescence change signal of the interfering gas is a recoverable response). Therefore, the detection of sarin can be determined based on the response of the sensing array composed of the two materials. (Note that the rising response R is a positive value, and the falling response R is a negative value. For material 1, only the falling part of the response to HF is calculated, and for material 2, only the rising part of the response to DCP, HCl, and HF is calculated).

[0204] The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. An organic fluorescent sensing array, characterized in that, The described organic fluorescent sensing array is composed of two types of organic fluorescent compound co-assembled sensing materials arranged together. The first type of organic fluorescent compound co-assembled sensing material is obtained by co-assembling the compound shown in formula (A) and the compound shown in formula (B), and the second type of organic fluorescent compound co-assembled sensing material is obtained by co-assembling the compound shown in formula (A) and the compound shown in formula (C). （A） （B） （C） in, s is an integer selected from 3 to 6; n is an integer selected from 1 to 3; m is an integer selected from 1 to 3; Each R is either the same or different, and is selected independently from C. 1-12 alkyl; Each R1 is either the same or different, and is independently selected from C. 1-12 Alkoxy or C 1-12 alkyl; Each R2 is either identical or different, and is independently selected from C. 1-12 alkyl; Each R3 may be the same or different, and is selected independently from C. 1-12 alkyl; R4 is selected from O or S.

2. The organic fluorescent sensing array according to claim 1, characterized in that, Each R is either the same or different, and is selected independently from C. 1-10 alkyl; Each R1 is either the same or different, and is independently selected from C. 1-10 Alkoxy or C 1-10 alkyl; Each R2 may be the same or different, and is independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, nonyl, or decyl; Each R3 may be the same or different, and is independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, nonyl, or decyl; R4 is selected from O or S.

3. The organic fluorescent sensing array according to claim 1 or 2, characterized in that, Each R may be the same or different, and is independently selected from one of the following groups: R1 is selected from one of the following groups: in This is the connection point; s is 3; m is 1; n is 1.

4. The organic fluorescent sensing array according to claim 1, characterized in that, In the organic fluorescent sensing array, the first organic fluorescent compound co-assembled sensing material is obtained by co-assembling the compound shown in formula (A) and the compound shown in formula (B) in molar ratios of 5:1, 10:1, 20:1, 50:1, 100:1, and 500:

1. The second organic fluorescent compound co-assembled sensing material is obtained by co-assembling the compound shown in formula (A) and the compound shown in formula (C) in molar ratios of 5:1, 10:1, 20:1, 50:1, 100:1, and 500:

1.

5. The organic fluorescent sensing array according to claim 1, characterized in that, In the organic fluorescent sensing array, the number of sensing materials co-assembled by the first and second organic fluorescent compounds is at least one. When the total number of sensing materials co-assembled by the two organic fluorescent compounds is three or more, the two are arranged sequentially.

6. The method for preparing the organic fluorescent sensing array according to any one of claims 1-5, characterized in that, Includes the following steps: (1) Prepare the compound shown in formula (A); (2) Prepare the compound shown in formula (B); (3) Prepare the compound shown in formula (C); (4) Dissolve the compound shown in formula (A) and the compound shown in formula (B) in a good solvent, and then add a poor solvent to co-assemble the first organic fluorescent compound co-assembled sensing material; dissolve the compound shown in formula (A) and the compound shown in formula (C) in a good solvent, and then add a poor solvent to co-assemble the second organic fluorescent compound co-assembled sensing material. (5) The two fluorescent materials obtained by co-assembly are coated on different positions of the same carrier to obtain the organic fluorescent sensing array; The preparation of the compound shown in formula (A) in step (1) includes the following steps: (A-1) Compound a1 reacts with a2 to give compound a3; (A-2) Compound a4 reacts with RX to give compound a5; (A-3) Compound a6 reacts with RX to give compound a7; (A-4) Compound a7 reacts with dipentanoyl diborone to give compound a8; (A-5) Compound a8 reacts with a3 to give compound a9; (A-6) Compound a9 undergoes ring-opening desulfurization to yield compound a10; (A-7) Compound a10 reacts with orthoformate ester to give compound a11; (A-8) Compound a11 reacts with compound a5 to give the compound shown in formula (A); Wherein, X is a halogen, and s, R, and R1 have the definitions described in any one of claims 1-3; The preparation of the compound shown in formula (B) in step (2) includes the following steps: (B-1) Compound b1 reacts with dipentanoyl diborone to give compound b2; (B-2) Compound b3 reacts with RX to give compound b4; (B-3) Compound b5 reacts with XR2 to give compound b6; (B-4) Compound b6 reacts with dipentanoyl diborone to give compound b7; (B-5) Compound b7 reacts with b4 to give compound b8; (B-6) Compound b8 reacts with compound b2 to give the compound shown in formula (B); Wherein, X is a halogen, and m, R, and R2 have the definitions described in any one of claims 1-3; The preparation of the compound shown in formula (C) in step (3) includes the following steps: (C-1) Compound c1 reacts with RX to give compound c2; (C-2) Compound c3 reacts with XR3 to give compound c4; (C-3) Compound c4 reacts with dipentanoyl diborone to give compound c5; (C-4) Compound c5 reacts with c2 to give compound c6; (C-5) Compound c6 reacts with dipentanoyl diborone to give compound c7; (C-6) Compound c7 reacts with 2,7-dibromofluorenone or 2,7-dibromo-9H-fluoren-9-thionone to give the compound shown in formula (C); Wherein, X is a halogen, and n, R, and R3 have the definitions described in any one of claims 1-3; The good solvent mentioned in step (4) is a haloalkane solvent; the bad solvent is an alkane solvent.

7. The preparation method according to claim 6, characterized in that, The carrier is a quartz tube or a glass tube.

8. The application of the fluorescence sensing array according to any one of claims 1-5 in distinguishing and detecting sarin and interfering gases; The interfering gas is selected from sarin analogues, volatile acids, or volatile small organic molecules; The sarin analogue is selected from at least one of diethyl chlorophosphate, diisopropyl fluorophosphate, and diethyl cyanophosphate; The acid is selected from at least one of hydrochloric acid, hydrofluoric acid, and acetic acid; The volatile organic molecules include toluene, n-hexane, dichloromethane, or methanol.

9. The application according to claim 8, characterized in that, The detected sarin concentration ranged from 50 ppb to above.

10. A portable device for rapid detection and differentiation of sarin, characterized in that, Includes the organic fluorescent sensing array according to any one of claims 1-5.

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