Silicon fluorene ptycene aromatic ether amine copolymer fluorescent probe as well as preparation method and application thereof

Abstract

The embodiment of the invention relates to a silafluorene ptycene aromatic ether amine copolymer fluorescent probe as well as a preparation method and application thereof, and belongs to the technical field of fluorescent probes. The preparation method of the silafluorene ptycene aromatic ether amine copolymer fluorescent probe provided by the embodiment of the invention comprises the following step: polymerizing three monomers A, B and C containing silafluorene, ptycene and aromatic ether amine with tripyridine as an end-capping structure to obtain the silafluorene ptycene aromatic ether amine copolymer fluorescent probe. The silafluorene ptycene aromatic ether amine copolymer fluorescent probe provided by the embodiment of the invention can be used for detecting various explosives, in the detection process, the fluorescence quenching amplification effect is utilized, the detectable sensitivity is very high and can reach the sensitivity limit lower than 0.1 ng (in terms of TNT), pure explosives can be continuously tested for at least 200 times, and the silafluorene ptycene aromatic ether amine copolymer fluorescent probe is not damaged after being recycled. The system is suitable for on-site alarm and steam induction in various harsh environments, and has the advantages of fast response, recoverability, high sensitivity, wide detection range and strong anti-interference capability.

Description

Technical Field

[0001] The embodiments of the present application relate to the technical field of fluorescent probes, and in particular to a silafluorene aromatic ether amine copolymer fluorescent probe and a preparation method and application thereof. Background Art

[0002] Due to the continuous development and wide variety of high energy density materials, their universal identification is very challenging. Energetic compounds, such as explosives, propellants and fireworks, are materials that can undergo violent chemical reactions and release large amounts of heat, pressure and gas in military and civilian applications. At present, social security is still facing severe pressure, terrorist cases occasionally occur, and the above-mentioned dangerous goods are typical materials for committing crimes. Common ones such as nitroaromatics, nitroesters, nitramines and nitroalkanes and black powder or energetic explosives mixed with different proportions of various of the above materials often appear in many fields and are also easily used by criminals. They are often white and odorless, and their vapor pressure is also extremely low. They are toxic and harmful to the environment and difficult to simply identify. Although they provide great value to society, they are also a weapon for committing crimes. Therefore, the identification of energetic compounds is of great significance in the fields of national security and environmental monitoring.

[0003] For this reason, it is particularly important to prepare a variety of sensors to detect these energetic hazardous materials. In particular, compared with other testing methods, fluorescent polymers (Conjugated Polymers, CPs) can achieve the same sensitivity as well-trained dogs due to their own advantages, and are low-cost, easy to make, easy to use, and can also test explosive vapors, providing the basic conditions for the development of a variety of on-site detection instruments and security gate modules and explosion detection instruments for high-speed rail stations, aircraft and aerospace airports, passenger bus stations, nuclear power plants, and major conference sites, and realizing fluorescent sensing of energetic explosive gases. Saturated vapor pressure of common explosives and detection limits of different instruments are as follows: Figure 1 shown.

[0004] In nitroaromatics, nitrates, nitramines and nitroalkanes high explosives, nitroaromatics (TNT, DNT [2,4-DNT, 2,6-DNT, etc.], MNT [o-NT, m-NT, p-NT], NB, TNB [vic-TNB, unsym-TNB, sym-TNB], DNB [o-DNB, m-DNB, p-DNB], NB, PA / TNP-PicricAcid, SA-Styphic Acid, DNP [2,4-DNP], Tetryl, DNAN); nitrates (EGDN, TEGDN, NG, PETN, ETN); nitramines (EDNA / Haleite / Explosive H, Tetryl, RDX, HMX) and nitroalkanes-liquid explosives (NM, NE, NP, DDBu / DMNB); contain one or more nitro groups, lack electrons themselves, and can be complexed with electron-rich ones, that is, produce dipole-dipole interactions, making it possible to detect them. In terms of mixed military high-energy explosives, such as ammonium ladder explosives (Amatol) containing TNT, Comp B, C2, C3, C4, PTX-1, PTX-2, Cyclotol with TNT and RDX as the main components, Detasheet, Pentolite containing PETN, Octol, Tetrytol are constructed with a large amount of TNT. The development of detection materials for the above-mentioned basic energetic explosives can be widely promoted and applied to a variety of mixed military explosives. In addition, for example, 8701, 8702, PW0, and PW30 independently developed by my country also use RDX as the main matrix. Some heat-resistant explosives with benzene ring as the matrix, such as single heat-resistant explosive triaminotrinitrobenzene (TATB), 2,2',4,4',6,6'-hexanitrostilbene (HNS), 2,6-bis(bitteramino)-3,5-dinitropyridine (PYX), high-temperature heat-resistant explosives, such as 5,5'-bis(2,4,6-trinitrophenyl)-2,2'-bis(1,3,4-oxadiazole) (TKX-55), 2-fluoro-1,3,5-triamino-4,6-dinitrobenzene (ZXC-8), hydroxylamine salt of PYX, etc., all exist in the form of polynitroaromatic hydrocarbons with a structure similar to TNT. By detecting nitroaromatic high-energy explosives, the test of this type of high-energy explosives, CL-20, ONC, TNTAC also belong to nitroalkanes and can also be extended to test. For the convenience of warning people, some of the above-mentioned explosives may also be added with DMNB as a label indicator. By testing DMNB, the presence of the above-mentioned mixed energetic explosives can be detected, which can further reduce false alarms and increase test accuracy.

[0005] In view of these aspects, the development of materials that can be widely used to test explosives appears to have great advantages. Since Professor Timothy M. Swager proposed the polymer fluorescence quenching amplification effect (Chemical Sensors Based on Amplifying Fluorescent Conjugated Polymers, Chem. Rev. 2007, 107, 1339-1386), many researchers have proposed various polymer structures represented by PA, PPP, PPV, PPy, PT, PPE, PANI, and PF. For example, the pioneer Swager first published in JACS (Fluorescent Porous Polymer Films as TNT Chemosensors: Electronic and Structural Effects, J. Am. Chem. Soc. 1998, 120, 11864-11873 and Porous Shape Persistent Fluorescent Polymer Films: An Approach to TNT Sensory The PPE type polymer represented by the ptercene skeleton published in Materials, J. Am. Chem. Soc. 1998, 120, 5321-5322) can sensitively detect extremely small amounts of TNT.Based on the similarity of pyrene structure with nitroaromatic hydrocarbons and the unique interaction discovered after long-term research, the fluorescent conjugated polymer film obtained by functionalizing the PPE main chain with pyrene groups, represented by Professor Fang Yu (Academician) of Shaanxi Normal University, can greatly improve the quenching response to TNT aqueous solution (Pyrene-Containing Conjugated Polymer-Based Fluorescent Films for Highly Sensitive and Selective Sensing of TNT in Aqueous Medium, Macromolecules. 2011, 44, 12, 4759-4766). Another example is the various small molecule dimers (oligomers) with fluorene as the parent core published by Professor Cheng Jiangong of the Shanghai Institute of Microsystem and Information Technology of the Chinese Academy of Sciences, such as Femtogram Level Detection of Nitrate Ester Explosives via an 8-Pyrenyl-Substituted Fluorene Dimer Bridged by a 1,6-Hexanyl Unit(ACSAppl.Mater.Interfaces,2014,6,8817-882),Direct and ultrasensitivefluorescence detection ofPETN vapor based on a fuorene-dimer probe via asynergic backbone and side-chain tuning(Anal.Methods.2018,10,2567),Aselective and stepwise aggregation of a new fluorescent probe for dinitrateexplosive differentiation by self-adaptive host-guest interaction(Sci.ChinaChem.2020,63,116-125),It has a specific characteristic reaction to one of the various nitrate explosives such as PETN, NG, MN, TEGDN, EGDN, or multiple nitrate explosives, which can reach the lowest level of mM (liquid) or ppt (vapor), 0.5fg / cm. 2In addition, Zhao Jincai and Che Yanke, researchers from the Beijing Institute of Chemistry, Chinese Academy of Sciences. A variety of oligomeric nanofiber sensing probes based on fluorene (carbazole) cores have been developed for various aromatic nitro groups, nitrates, nitrate esters, nitramines and nitroalkanes, and sulfur-containing (gunpowder) energetic explosives, such as Fluorescence Detection of a Broad Class of Explosives with One Zinc (II)-Coordination Nanofiber (Anal. Chem. 2016, 88, 22, 10826-10830), Discrimination of Five Classes of Explosives by a Fluorescence Array Sensor Composed of Two Tricarbazole-Nanostructures (Anal. Chem. 2017, 89, 22, 11908-11912), Interpenetrated Binary Supramolecular Nanofibers for Sensitive Fluorescence Detection of Six Classes of Explosives (Anal. Chem. 2018, 90, 7, 4273-4276), Kinetic Stable Nanoribbons with Improved Exciton Migration Length for Detecting Explosives (ACS Appl. Nano Mater. 2020, 3, 4880-4885), Emergent Photostability Synchronization in Coassembled Array Members for the Steady Multiple Discrimination of Explosives (Adv. Sci. 2022, 9, 2102739), have excellent LOD detection values ​​for a variety of explosives, and the lowest sensitivity limit can reach 0.1ng TNT. The above results provide a theoretical and practical basis for detecting various explosives by fluorescence quenching and then steam. However, there are still some shortcomings, and some have serious disadvantages. For example, due to the extremely low vapor pressure of PETN, NG, RDX, and HMX, it is difficult to be detected by steam, which is inconvenient for on-site detection, or the testing of the above energetic explosives cannot be repeated multiple times, resulting in only a single test. Therefore, it is of practical significance to develop a class of fluorescent probes with universality, fast response, recoverability, high sensitivity, wide detection range, and strong anti-interference ability. Summary of the invention

[0006] In view of this, the embodiments of the present application provide a silanol aromatic ether amine copolymer fluorescent probe and a preparation method and application thereof. The fluorescent probe can be used for the detection of a variety of explosives, such as ammonium antimony-Amatol, C4, and Comp B. During the detection process, the fluorescence quenching amplification effect is utilized to achieve a high detection sensitivity, which can reach a sensitivity limit of less than 0.1 ng (in terms of TNT), and the polymer itself can also resist photo-oxidative quenching (i.e., photobleaching) and slowly recover a certain fluorescence self-healing property under the test environment. Pure explosives can be continuously tested for at least 200 times, and can be recycled without being destroyed. It is suitable for on-site alarms and steam sensing in a variety of harsh environments, and has many advantages such as fast response, recoverability, high sensitivity, wide detection range, and strong anti-interference ability, which can effectively overcome the defects of the above-mentioned prior art.

[0007] In a first aspect, an embodiment of the present application provides a silanol aromatic ether amine copolymer fluorescent probe, wherein the structural formula of the silanol aromatic ether amine copolymer fluorescent probe is:

[0008]

[0009] Wherein, A and C are selected from the first monomer, the second monomer or the fifth monomer, and the first monomer, the second monomer and the fifth monomer are all diacetylene monomers; B is selected from the third monomer or the fourth monomer, and the third monomer and the fourth monomer are both dihalogen monomers;

[0010] a, b, and c represent the different numbers of monomers linked to the silanol aromatic ether amine copolymer.

[0011] In some embodiments that may include the above embodiments, the silanolpyrene aromatic ether amine copolymer fluorescent probe structure also includes a tripyridine end-capping structure, and its structural formula is:

[0012]

[0013] Wherein, D is a tripyridine-terminated structure.

[0014] In some embodiments that may include the above embodiments, the structural formula of the diacetylenic monomer is selected from one or more of the following:

[0015]

[0016] Wherein, X is C or Si, preferably Si; Y is O, N, NH or S, preferably O; R is H or alkyl C n H 2n+1 , and n is an integer between 1 and 25, and R2 represents two Rs.

[0017] In some embodiments that may include the above embodiments, the structural formula of the dihalogen monomer is selected from one or more of the following:

[0018]

[0019] Wherein, X is C or Si, preferably Si; Y is O, N, NH or S; R is H or alkyl C n H 2n+1 , and n is an integer between 1 and 25; R2 represents two Rs.

[0020] In some embodiments that may include the above embodiments, the structural formula of the tripyridine-terminated structure is selected from one or more of the following:

[0021]

[0022] Wherein, Z is Br or I, preferably I.

[0023] In some embodiments that may include the above embodiments, the structural formula of the silanol aromatic ether amine copolymer fluorescent probe is:

[0024]

[0025] Where R is H, alkyl C n H 2n+1 , alkenyl, alkynyl, fluorenyl or fluorenyl with heteroatom, and n is an integer within the range of 1-25; EDG is an electron donating group, which is OR, NR2 or PEG; R2 represents two Rs; M is C or Si.

[0026] The second aspect of the embodiment of the present application further provides a method for preparing the above-mentioned silanol-pterylene aromatic ether amine copolymer fluorescent probe, comprising the following steps:

[0027] A type of monomers A, B and C containing silymarine, pterygium and aromatic ether amine with tripyridine as the end-capping structure are polymerized to form a silymarine pterygium aromatic ether amine copolymer material based on tripyridine end-capping. The copolymer is then precipitated into a solid using methanol and chloroform to obtain the product. The molecular weight analysis and performance testing are then carried out to finally determine the feasible polymer-related parameters.

[0028] The third aspect of the embodiments of the present application also provides the use of the above-mentioned silanol aromatic ether amine copolymer fluorescent probe in detecting energetic substances.

[0029] Compared with the prior art, the embodiments of the present application have the following beneficial effects:

[0030] The polymer in the present application utilizes the characteristics of multi-conjugated polymers being electron-rich and nitro explosives being electron-deficient, and Si / O / N being NO2-philic (N / O being HNO3-philic), which can form acceptor-donor bonds through complex interaction, thereby causing the principle of polymer solid-state fluorescence changes. The polymer can be used to detect nitroaromatic hydrocarbons (NAC for short - including trinitrotoluene - TNT, dinitrotoluene - DNT, dinitrobenzene - DNB, nitrotoluene - MNT and nitrobenzene - NB and other similar nitroaromatic hydrocarbon explosives), nitroester explosives (NAE, nitroglycerin - NG, nitrate ester - PETN and other similar nitrate ester explosives), nitramine explosives, and the like. It can detect explosives (abbreviated as NAM - including RDX, HMX and other similar nitramine explosives), nitroalkanes (liquid explosives or explosive label indicators, nitromethane - NM, nitroethane - NE, nitropropane - NP, dinitrobutane - DDBu / DMNB), and has the ability to detect the analogues of the above four categories of explosives, such as picric acid - PA / TNP, Tetryl, and can also be used for black powder (S+2KNO3+3C) - including firecracker fuse powder and firecracker internal powder and granular gunpowder, as well as the detection of mixed explosives of the above components, such as ammonium antimony - Amatol, C4, Comp B. During the detection process, the fluorescence quenching amplification effect is used to achieve high detection sensitivity, which can reach a sensitivity limit of less than 0.1ng (in TNT). The polymer itself can also resist photo-oxidative quenching (i.e. photobleaching) and slowly recover a certain fluorescence self-healing property under the test environment. It can continuously test pure explosives for at least 200 times and can be recycled without damage. It is suitable for on-site alarms and steam sensing in a variety of harsh environments, and has many advantages such as fast response, recoverability, high sensitivity, wide detection range, and strong anti-interference ability. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0032] Figure 1 The saturated vapor pressure of common explosives and the detection limits of different instruments;

[0033] Figure 2 Schematic diagram of the reaction of the pterisene between the polymers of the present application to form a topologically ordered structure to TNT;

[0034] Figure 3 Schematic diagram for comparison of quenching amplification effect (small molecule-without and polymer-with);

[0035] Figure 4 For A31 H NMR: CDCl3 compound spectrum;

[0036] Figure 5 For A4 1 H NMR: CDCl3 compound spectrum;

[0037] Figure 6 For B1 1 HNMR: CDCl3 compound spectrum;

[0038] Figure 7 For P1 1 H NMR: CDCl3 compound spectrum;

[0039] Figure 8 For P2 1 H NMR: CDCl3 compound spectrum;

[0040] Fig. 9 is the spectrum of P1 APC compound;

[0041] Fig.10 This is the spectrum of P2 GPC 1 compound;

[0042] Fig.11 It is the spectrum of P2 GPC 2 compound;

[0043] Fig.12 is the solid UV absorption spectrum of polymer P2;

[0044] Fig.13 is the UV absorption spectrum of polymer P1;

[0045] Fig.14 is the UV absorption spectrum of polymer P2;

[0046] Fig.15 The fluorescence change diagram of the explosive TNT tested for P1;

[0047] Fig.16 This is the DNT fluorescence change diagram of the explosive tested by P1;

[0048] Fig.17 This is the fluorescence change diagram of MNT in the P1 test explosive;

[0049] Fig.18 It is the non-interference diagram of various solvents;

[0050] Fig.19 This is a graph showing that the instrument can run smoothly with the pumping time;

[0051] Fig. 20 It is the real-time response signal diagram of pure nitromethane, nitroethane and dinitrobutane;

[0052] Fig.21 It is the real-time response signal diagram of dinitrotoluene and nitrotoluene vapor;

[0053] Fig. 22 It is the real-time response signal diagram of picric acid vapor;

[0054] Fig.23 This is the real-time response signal diagram of dinitroaniline (uncommon explosive) vapor;

[0055] Fig.24 Real-time response signal diagram for NG and PETN steam;

[0056] Fig.25 Real-time response signal diagram for RDX and HMX steam;

[0057] Fig.26 It is the real-time response signal diagram of dinitrobenzene and nitrobenzene vapor;

[0058] Fig. 27 It is tested for multiple different steam and can recover the fluorescence image;

[0059] Fig.28 Tested for TNT and Tetryl and recoverable fluorescence images;

[0060] Fig.29 Real-time response signal graphs for silver black powder and granular black powder vapor testing;

[0061] Fig.30 Real-time response signal diagram for C4 and ammonium-titrate explosive vapor testing;

[0062] Fig.31 This is the real-time response signal diagram of 0.1ng TNT test steam. DETAILED DESCRIPTION

[0063] In order to make the purpose, technical solution and advantages of the embodiments of the present application clearer, the technical solution in the embodiments of the present application will be clearly and completely described below in conjunction with the drawings in the embodiments of the present application. Obviously, the described embodiments are part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of this application.

[0064] (1) Fluorescence detection principle of this application:

[0065] 1. First of all, the electron-rich polymer molecule PPE-TPFP is a multi-conjugated compound containing multiple aromatic rings (benzene rings) and triple bonds, which can form π electron delocalization and have multiple long-chain alkyloxy groups to donate electrons, so it has strong fluorescence with an absorption wavelength of 390-440nm and an excitation wavelength of about 440-630nm (wavelength red shift). In addition, due to the rigid skeletons of pterene and spirofluorene silicon, by adding heteroatom nitrogen and oxygen chains, they can prevent them from stacking with each other to form a rod-like stacked structure, which helps to weaken their aggregation-induced fluorescence quenching (ACQ), thereby meeting the basic conditions for achieving fluorescence detection.

[0066] 2. Secondly, nitroaromatic hydrocarbons (polynitroaromatic compounds), oxygen-containing acid salts (ammonium nitrate, ammonium picrate, urea nitrate, and other similar nitrate explosives), nitroester explosives (nitroglycerin, nitrate esters and other nitrate ester explosives), nitramine explosives (RDX, octogen), have multiple electron-deficient nitro functional groups, which can be heated and decomposed into nitrogen dioxide under certain conditions, and further form nitric acid. The terminal functional groups of polymer pyridine can react to nitrogen dioxide or the generated nitric acid. The explosives contain NO2 and decompose into NO2 as shown below:

[0067]

[0068] The reaction of the pyridine end in the silanolpyruvyl aromatic ether amine copolymer fluorescent probe of the present application to nitrogen dioxide and nitric acid is shown as follows:

[0069]

[0070] Because the polymer structure of the present application has many oxygen side chains that donate electrons, nitroaromatic hydrocarbons (polynitroaromatic compounds), nitroester explosives (nitroglycerin, nitrate esters and other nitrate ester explosives), and nitramine explosives (RDX, octogen and other similar nitramine explosives) are electron-deficient and can evaporate under high-temperature heating conditions. Due to van der Waals forces, they can be complexed with the electron-rich molecule PPE-TPFP to produce donor-acceptor bonds, weaken its electron density, and change the fluorescence emission intensity of PPE-TPFP, thereby realizing the detection of such explosives. For example: NG, PETN, TEGDN, EGDN and ETN (Erythritol Tetranitrate) have nitro groups at the ends of their nitrate chains, which can be complexed and identified by electron-rich molecules. The schematic diagram of the interaction between the silanol phthalene aromatic ether amine copolymer fluorescent probe of the present application and Taian is shown below:

[0071]

[0072] In particular, the silicon of some silicon-substituted fluorenes also has a weak interaction with the nitro group, which can increase the probability and intensity of polymer fluorescence change. The interaction between silicon-containing polymers and trinitrotoluene or RDX is shown below:

[0073]

[0074] 4. The polymers of the present application are arranged to form a topological structure due to the pterene skeleton and the polycarbonate ether chain, which avoids aggregation-induced fluorescence quenching (ACQ), so as to further form a gas path to promote the entry of explosive molecules and limit the entry of other non-compliant molecules (too large in size). The reaction of pterene to TNT in a topologically arranged ordered structure is shown in the following figure: Figure 2 shown.

[0075] 5. This detection reaction also utilizes the fluorescence amplification effect (quenching amplification effect) process. The fluorescence amplification effect quenching amplification effect is called the "molecular wire" effect or the "one point contact, multiple points response" effect. The comparison of the quenching amplification effect (small molecule-without and polymer-with) is shown below. Figure 3 shown.

[0076] (2) Raw material sources and testing methods:

[0077] 1. Most of the main raw material monomers are outsourced and customized by reagent companies such as Anergy, McLean, Aladdin and Hequan Pharmaceuticals or directly commercially available. Only a small amount is synthesized by ourselves, as can be seen in the Examples section; the tested trinitrotoluene (TNT), dinitrotoluene (DNT), nitrotoluene (MNT), nitrobenzene (NT), ammonium nitrate (AN), nitroglycerin (NG), PETN, RDX, octogen (HMX), etc. are all from commercially available standard concentration substances.

[0078] 2. In CDCl3 solution, the Varian liquid NMR instrument (400MHz) of West Lake University was used to record the 1 HNMR and 13 C NMR spectra, chemical shifts are based on residual protonated solvent. TMS (δ = 0.00 ppm) was used as an internal reference. 1 H NMR spectrum; recorded using CDCl3 (δ = 77.00 ppm) / DMSO-d6 (δ = 39.52 ppm) as internal reference 13 C NMR spectroscopy. 1 H NMR and 13 C NMR peak type abbreviations: s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet, br = broad.

[0079] 3. Polymer testing uses Agilent APC and Agilent GPC to measure molecular weight (M w ,M n ,M z ) and polymer dispersibility index (PDI) were measured by high temperature H-NMR spectrum using a Varian liquid high temperature NMR instrument (400 MHz).

[0080] 4. All chemical related parts not described in detail in this application are conventional technical contents.

[0081] (3) Overall synthetic route:

[0082] Linear method (main) and convergent method synthesis. First, synthesize different monomers, then polymerize the monomers multiple times (in different orders) to obtain the required three-component polymer, and introduce polypyridine through the end-capping method. Through the monomers, control the catalyst ligand, add the amount of co-catalyst, and then control the time and temperature to synthesize polymers with different molecular weights and different structures. The linear synthesis route is shown below:

[0083]

[0084] (4) Implementation process of some typical molecules:

[0085] 1. Synthesis of Compound A1:

[0086]

[0087] General approach:

[0088] Take a 500mL three-necked flask, add a stirrer, and connect a double row of tubes for nitrogen protection. Add stirring A (10.0g, 50mmol) and anthracene (17.8g, 10mmol) solution to the flask. At room temperature, n-butyl lithium solution (126mmol) in anhydrous hexane (1000mL) was continuously added to the stirred mixture, and the reaction was continued for 10 hours in a nitrogen stream. After the reaction was completed, the reaction mixture was quenched with methanol (100mL) under an ice-water bath. The reaction mixture was then concentrated on a rotary evaporator to obtain a yellow viscous solid. The product was separated by silica gel column chromatography, using hexane as an eluent, and the first part was unreacted anthracene (5g). Using toluene as an eluent, the second part was compound A1, and 0.56g (1.3mmol, 94% yield based on the consumed anthracene) was obtained. The product was recrystallized from carbon tetrachloride to obtain a colorless needle-shaped substance.

[0089]

[0090] 1H NMR: (CDCl3, 400MHz): δ (ppm) = δ7.0-7.3 (m, 10H), 6.68-7.0 (m, 8H), 5.18 (s, 4H); 13 C NMR: (CDCl3, 100MHz): δ (ppm) = δ145.03, 142.10, 124.67, 123.07, 119.40, 53.68; HRMS: C 34 H 22 (M+H + ),Calculate:430.17;Find 430.21.

[0091] 2. Synthesis of Compound A2:

[0092]

[0093] General approach:

[0094] In a 100 mL single-necked flask, NaIO4 (1.20 g, 5.6 mmol) and I2 (4.26 g, 16.8 mmol) were suspended in a stirred mixture of glacial acetic acid (20 mL) and acetic anhydride (10 mL) cooled to 5-10 ° C. Under vigorous stirring, concentrated sulfuric acid (98%, 5.32 mL, 9.8 g, 100 mmol) was slowly added dropwise while maintaining the temperature between 5-10 ° C (exothermic reaction). Subsequently, A1 (6.06 g, 14.0 mmol) was added and stirring was continued at room temperature for 5 hours. The reaction mixture was poured into ice water containing Na2SO3. After about 30 minutes, the precipitate obtained by collecting and filtering was A2 (8.12 g, 85%).

[0095]

[0096] 1 H NMR: (CDCl3, 400MHz): δ (ppm) = δ7.67-7.25 (m, 2H), 7.09 (dd, J = 5.9, 3.4Hz, 2H), 5.26 (d, J = 0.9Hz, 1H); 13 C NMR: (CDCl3, 100MHz): δ (ppm) = δ 144.82, 142.21, 141.16, 126.60, 126.47, 126.38, 88.55, 52.48.

[0097] 3. Synthesis of Compound A3:

[0098]

[0099] General approach:

[0100] Using a 100mL Shrek reaction bottle, Pd(PPh3)2Cl2(840mg, 1.2mmol) and CuI(360mg, 2.4mmol) were dissolved in diethylamine (150mL) at room temperature. A2(8.11g, 11.88mmol) was added to the solution, and the mixed solution was then cooled to 0°C. Next, trimethylsilyl acetylene (5.04mL, 35.4mmol) was added for treatment. The reaction solution was heated to room temperature and stirred at this temperature for 12 hours. After the reaction was completed, the solvent was removed by vacuum evaporation. The crude product was eluted with hexane on a silica gel column to obtain yellow solid compound A3(6.83g, 92%).

[0101]

[0102] 1 H NMR: (CDCl3, 400MHz): δ (ppm) = δ7.35 (m, 8H), 6.92 (m, 8H), 5.50 (s, 4H), 0.19 (s, 18H); IR (thin film, neat, KBr): cm -1 :3498,3257,3068,3019,2959,2897,2173.

[0103] 4. Synthesis of Compound A4:

[0104]

[0105] General approach:

[0106] In a 250mL three-necked flask, compound A3 (8.4g, 47.13mmol) was dissolved in a mixed solution of 90mL tetrahydrofuran (THF) and 90mL methanol (MeOH), followed by a solution of 6.0g potassium hydroxide (KOH) dissolved in 20mL water. The mixture was stirred at room temperature for 6 hours, and the reaction progress was monitored by thin layer chromatography (TLC) (developing solvent: hexane / dichloromethane = 3:1). After the reaction was completed, the obtained solid was filtered and washed with water and hexane. The product was finally dried in a vacuum oven to obtain a white powder solid compound A4 (6.2g, 95%).

[0107]

[0108] 1 H NMR: (CDCl3, 400MHz): δ (ppm) = δ7.34-7.35 (m, 8H), 6.92-6.97 (m, 8H), 5.82 (s, 4H), 3.70 (s, 2H).

[0109] 5. Synthesis of Compound B1:

[0110]

[0111] Y=O,n=1,R=C 14 H 29 ;

[0112] General approach:

[0113] Take a 250mL three-necked flask, B (5.00g, 13.8mmol), 1-iodotetradecane (7.8mL, 28.8mmol, ρ=1.165g / mL) and dry K2CO3 (25.00g, 181mmol) are placed in a round-bottom flask and dried in a vacuum at 90°C. Under an argon atmosphere, the mixture is dissolved in DMF (200mL). The reaction mixture is stirred at 100°C for 18 hours. The mixture is diluted with EtOAc and washed with brine. The organic layer is separated and dried with anhydrous Na2SO4. Evaporated by a rotary evaporator to remove the solvent, and the residue is purified by silica gel column chromatography (n-Hex:CH2Cl2=19:1) to obtain B1 (8.85g, 92%) as a white solid.

[0114]

[0115] The synthesis methods of other R groups are the same, and only the equivalent weight needs to be adjusted for synthesis.

[0116] 1 H NMR: (CDCl3, 400MHz): δ (ppm) = δ7.17 (s, 2H), 3.92 (t, J = 6.4Hz, 4H), 1.79 (m, J =6.7Hz, 4H), 1.49 (m, J = 7.2Hz, 4H), 1.37-1.23 (m, 40H), 0.88 (t, J = 6.9Hz, 6H).

[0117] 6. Synthesis of Compound C1:

[0118]

[0119] Y=N,n=2,R=C 12 H 25 ; C is outsourced and customized from Anage, McLean, Aladdin and Hequan Pharmaceuticals.

[0120] General approach:

[0121] The material C (1.08 g, 3.0 mmol) was dissolved in 50 mL of dry THF in a 500 mL round bottom flask equipped with a magnetic stirrer and a reflux condenser. 4.05 g (21 mmol) of 1-bromooctane and 250 μL of 15-crown-5 were added to the solution. Subsequently, 800 mg (60%, 4.2 mmol) of solid oil-coated sodium hydride was slowly added. The mixture was reacted under reflux for 3 days. After the reaction was completed, the reaction was quenched with 100 mL of water and the organic product was extracted with ether (3×100 mL). The combined organic layer was dried over anhydrous MgSO4 and filtered. The solvent was removed by rotary evaporation to obtain a crude product, which was precipitated using PE and EtOH to obtain a relatively pure off-white solid, and then purified by column chromatography (developing solvent: hexane, the column was wrapped with aluminum foil to avoid light), ultimately obtaining 1.86 g of the desired product C1 (1.86 g, yield 60%) as a pure white solid powder.

[0122]

[0123] The synthesis methods of other R groups are the same, and only the equivalent weight needs to be adjusted for synthesis.

[0124] 1 H NMR: (CDCl3, 400MHz): δ (ppm) = δ7.46 (s, 2H), 3.27 (t, J = 6.1Hz, 8H), 1.41 (m, 8H), 1.38-1.21 (m, 72H), 0.94-0.85 (m, 12H); 13 C NMR: (CDCl3, 100MHz): δ (ppm) = δ 150.3, 134.4, 101.7, 54.7, 32.1, 29.6, 29.5, 29.3, 29.2, 27.7, 27.5, 27.3, 27.2, 22.9, 14.4. HRMS:C 54 H 102 I2N2(M+H)+,Calculate:1033.61;Find:1033.59.

[0125] 7. Synthesis of Compound P1:

[0126]

[0127] B2 is the above B1: Y = O, n = 1, R = C 14 H 29 The specific substituted molecules, R'=CH3; D comes from outsourcing customization of Anergy, McLean, Aladdin and Hequan Pharmaceuticals.

[0128]

[0129] General approach:

[0130] Use two Shrek reaction bottles and pre-fill ( i Pr2NH:Tol.=2:8) was placed in a 50mL Schlenk reaction bottle that was dried and filled with nitrogen. Nitrogen was bubbled to remove oxygen. Diethynylpentacyclopentene A4 (460mg, 0.96mmol), 1,4-diiodo-2,3-di(n-tetradecyloxy)benzene (B2, 725mg, 0.96mmol), Pd(PPh3)4 (115mg, 0.096mmol) and CuI (115mg, 0.0603mmol) were placed in another 250mL Schlenk flask. The flask was degassed and backfilled with argon three times, and 30mL of oxygen-free solvent ( i Pr2NH:Tol.=2:8). The mixture was heated at 70°C for 2 days. While hot and under the protection of high-pressure nitrogen flow, Pd(PPh3)4 (115 mg, 0.096 mmol) and CuI (115 mg, 0.0603 mmol), D (248 mg, 0.96 mmol) were weighed and quickly added. The mixture was heated at 70°C for another 2 days, cooled to room temperature, and the solvent was removed. The solid was dissolved in dichloromethane, washed with aqueous ammonium chloride to remove copper ions, and dried with Na2SO4. The solvent was removed in vacuo, and the residue was reprecipitated from dichloromethane into methanol, and the dissolution and precipitation were repeated many times. The yellow solid was collected by filtration to obtain polymer P1 (988.77 mg, 69%).

[0131] Y=N,n=2,R=C 12 H 25 , R'=CH3; D is outsourced from Anage, McLean, Aladdin and Hequan Pharmaceuticals; the method of using C2 for synthesis is the same as above, but the required polymerization time is longer, up to 7 days, and the required temperature is higher, up to 90°C, because its N atom causes the polymer polymerization degree to be low, which has a harmful effect on the cross-coupling reaction.

[0132]

[0133] P1: 1 H NMR: (CDCl3, 400MHz): see attached Figure 7 ;APC:M w ,M n,Percent:20048,1618,42.42%;12679,1713,8.13%;10821,1784,8.45%;9035,1810,8.83%;7 310,1777,8.91%; 5673,1657,8.53%; 4188,1431,7.17%; 2922,1082,5.03%; 1890,649,2.54%.

[0134] 8. Synthesis of compound P2:

[0135]

[0136] Specifically: containing end-capping, wherein the example is to replace B described in 7 with: Y=O, n=1, R=C 14 H 29 , R'=CH3; D is outsourced and customized from Anergy, McLean, Aladdin and Hequan Pharmaceuticals, and E is commercially available.

[0137] Specifically: containing end capping, wherein the example is to replace B described in 7 with: Y = N, n = 2, R = C 12 H 25 , R'=CH3; D is outsourced and customized from Anergy, McLean, Aladdin and Hequan Pharmaceuticals, and E is commercially available, similar to the above.

[0138] General approach:

[0139] Continue the operation in step 7, and finally continue to weigh and quickly add E (419.8 mg, 0.96 mmol) while hot and under the protection of high-pressure nitrogen flow, and heat the mixture at 70 ° C for another 3 days, cool to room temperature, and remove the solvent. The solid is dissolved in dichloromethane, washed with aqueous ammonium chloride to remove copper ions, and dried with Na2SO4. The solvent is removed in vacuo, and the residue is reprecipitated from dichloromethane into methanol, and the dissolution and precipitation are repeated many times. The yellow solid material is collected by filtration to obtain polymer P2 (1101.3 mg).

[0140] P2: 1 H NMR: (CDCl3, 400MHz): see attached figure; GPC: M w ,M n ,PDI:13688,10999,1.51; 13469,8400,1.84.

[0141] (5) Spectra of some compounds:

[0142] Figure 4 For A3 1 H NMR: CDCl3 compound spectrum; Figure 5 For A41 H NMR: CDCl3 compound spectrum; Figure 6 For B1 1 HNMR: CDCl3 compound spectrum; Figure 7 For P1 1 H NMR: CDCl3 compound spectrum; Figure 8 For P2 1 HNMR: CDCl3 compound spectrum; Fig. 9 is the spectrum of P1 APC compound; Fig.10 This is the spectrum of P2 GPC 1 compound; Fig.11 This is the spectrum of the P2GPC 2 compound. The polymer molecular weight Mn is in the range of about 10,000-20,000 (containing about 10-20 polymerization units), the PDI is narrow, and the detailed structure of the polymer can be seen in the synthetic spectrum. The synthesized polymer is more suitable for explosive experimental research.

[0143] (6) Fluorescence test data:

[0144] 1. PPE-TPFP (P2) solid UV absorption spectrum is as follows Fig.12 As shown, the optimal absorption wavelength of polymer solid is about below 480nm.

[0145] 2. According to the test results, select P2, acrylic substrate spin coating, 1mg / mL, and the best absorption wavelength is 390-440nm for fluorescence correlation test. The results are as follows Fig.13 and Fig.14 As shown, the optimal absorption wavelength of the obtained polymer is about 425nm, and the excitation wavelength is about above 450nm, based on which the optimal experimental conditions can be selected.

[0146] 3. P2, acrylic substrate spin coating, 1 mg / mL, at 425 nm excitation wavelength, under heating conditions (100 ° C), the results of explosives TNT, DNT, MNT fumigation / unfumigation are as follows Figure 15-17 As shown in the figure, the polymer exhibits a violent fluorescence quenching reaction when exposed to explosives, and it responds very quickly to the explosive vapor within 3s to 5s.

[0147] Note: exc_x nm represents x nm test under heating condition (100℃), exc_x nm_y s represents ys test of fumigated explosive under heating condition (100℃). For example, exc_420nm represents 420nm test under heating condition (100℃), and 1mg / mL concentration is spin-coated for excitation, and the same applies to others; exc_420nm_5s represents 420nm fumigated explosive test under heating condition (100℃) for 5s, and 1mg / mL concentration is spin-coated for excitation, and the same applies to others.

[0148] (7) Explosive response data:

[0149] Test method:

[0150] 1. Solution preparation: Use chloroform as solvent to prepare a 5 mg / mL solution of PPE-TPFP (P2), attach it to the acrylic substrate by dropwise injection, and then age it in an oven at 100°C for 1 hour before use.

[0151] 2. Thin film preparation: Use the test equipment and auxiliary components described in our company's patent CN105866091A / CN201720381260.7 / CN214584899U, spin the G solution on a quartz wafer (Φ=5mm) at a speed of 1500rpm / min on a spin coater for a total time of 5s. After the thin film is made, it is used. It is also considered to cover it with spin coating once more, for a total of two times.

[0152] 3. Temperature dependence: The fluorescence spectra were measured at different temperatures. As the temperature increased, the fluorescence intensity of the film increased slightly and then slowly decayed. When the internal cavity temperature was 80°C, the fluorescence intensity of the film decreased by 30%, and then continued to slowly decrease to approach the initial value, and then stabilized. This result proves that the film is stable to temperature and air.

[0153] 4. Test results: Test the response images of different types of explosives. Figure 18-31 As shown, the obtained polymer exhibits sensitive fluorescence response to various explosives and reacts rapidly, which is suitable for rigorous field testing.

[0154] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit it. Although the present application has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present application.

Claims

1. A silanol-pterylene aromatic ether amine copolymer fluorescent probe, characterized in that: The structural formula of the silanol aromatic ether amine copolymer fluorescent probe is: Wherein, A and C are selected from the first monomer, the second monomer or the fifth monomer, and the first monomer, the second monomer and the fifth monomer are all diacetylene monomers; B is selected from the third monomer or the fourth monomer, and the third monomer and the fourth monomer are both dihalogen monomers; a, b, and c represent the different numbers of monomers linked to the silanol aromatic ether amine copolymer.

2. The silanol-pterylene aromatic ether amine copolymer fluorescent probe according to claim 1, characterized in that: The silanolpyrene aromatic ether amine copolymer fluorescent probe structure also includes a tripyridine end-capping structure, and its structural formula is: Wherein, D is a tripyridine-terminated structure.

3. The silanol-pterylene aromatic ether amine copolymer fluorescent probe according to claim 1, characterized in that: The structural formula of the diacetylenic monomer is selected from one or more of the following: Wherein, X is C or Si; Y is O, N, NH or S; R is H or alkyl C n H 2n+1 , and n is an integer between 1 and 25, and R2 represents two Rs.

4. The silanol-pterylene aromatic ether amine copolymer fluorescent probe according to claim 1, characterized in that: The structural formula of the dihalogen monomer is selected from one or more of the following: Wherein, X is C or Si; Y is O, N, NH or S; R is H or alkyl C n H 2n+1 , and n is an integer between 1 and 25; R2 represents two Rs.

5. The silanol-pterylene aromatic ether amine copolymer fluorescent probe according to claim 2, characterized in that: The structural formula of the tripyridine-terminated structure is selected from one or more of the following: Wherein, Z is Br or I.

6. The silanol-pterylene aromatic ether amine copolymer fluorescent probe according to claim 2, characterized in that: The structural formula of the silanol aromatic ether amine copolymer fluorescent probe is: Where R is H, alkyl C n H 2n+1 , alkenyl, alkynyl, fluorenyl or fluorenyl with heteroatom, and n is an integer within the range of 1-25; EDG is an electron donating group, which is OR, NR2 or PEG; R2 represents two Rs; M is C or Si.

7. A method for preparing the silanol-pterylene aromatic ether amine copolymer fluorescent probe according to any one of claims 2 to 6, characterized in that: The following steps are involved: A type of monomers A, B and C containing silymarine, pterygium and aromatic ether amine with tripyridine as the end-capping structure are polymerized to form a silymarine pterygium aromatic ether amine copolymer material based on tripyridine end-capping. The copolymer is then precipitated into a solid using methanol and chloroform to obtain the product. The molecular weight analysis and performance testing are then carried out to finally determine the feasible polymer-related parameters.

8. Use of the silafluorene aromatic ether amine copolymer fluorescent probe according to any one of claims 1 to 6 in detecting energetic substances.

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