Cooperative Supramolecular Polymerization of Propeller-Shaped Triphenylamine Cyanostilbenes for Explosive Detection

Self-assembly ofπ-conjugated compounds into supramolecular polymers has received considerable attention because of their intrinsic scientific interests and technological applications.As compared toπ-conjugated rods,discotics,and macrocycles,propeller-shapedπ-conjugated molecules have been less exploited to form long-range-ordered supramolecular polymers.Herein a novel type of supramolecular polymers has been constructed on the basis of propeller-shaped triphenylamine cyanostilbenes.The designed compound adopts nucleation-elongation cooperative mechanism for the supramolecular polymerization process,because of the participation of three-fold hydrogen bonds between the neighbouring monomers.The supramolecular polymeric state displays amplified chirality and enhanced emission than those in the monomeric state.The resulting supramolecular polymers exhibit severe emission quenching upon addition of 2,6-dinitrotoluene,ascribed to photoinduced electron transfer from the triphenylamine cyanostilbenes to the explosive analyte.The current study proves the feasibility to supramolecular polymerize propeller-likeπ-conjugated molecules,serving as a promising type of explosive sensor owing to their guest encapsulation and signal amplification capabilities.

Matrix Effect on Polydiarylfluorenes Electrospun Hybrid Microfibers: From Morphology Tuning to High Explosive Detection Efficiency

Precisely optimizing the morphology of functional hybrid polymeric systems is crucial to improve its photophysical property and further extend their optoelectronic applications. The physic-chemical property of polymeric matrix in electrospinning (ES) processing is a key factor to dominate the condensed structure of these hybrid microstructures and further improve its functionality. Herein, we set a flexible poly(ethylene oxide) (PEO) as the matrix to obtain a series of polydiarylfluorenes (including PHDPF, PODPF and PNDPF) electrospun hybrid microfibers with a robust deep-blue emission. Significantly different from the rough morphology of their poly(N-vinylcarbazole) (PVK) ES hybrid fibers, polydiarylfluorenes/PEO ES fibers showed a smooth morphology and small size with a diameter of 1∼2 µm. Besides, there is a relatively weak phase separation under rapid solvent evaporation during the ES processing, associated with the hydrogen-bonded-assisted network of PEO in ES fibers. These relative “homogeneous” ES fibers present efficient deep-blue emission (PLQY>50%), due to weak interchain aggregation. More interestingly, low fraction of planar (β) conformation appears in the uniform PODPF/PEO ES fibers, induced by the external traction force in ES processing. Meanwhile, PNDPF/PEO ES fibers present a highest sensitivity than those of other ES fibers, associated with the smallest diameter and large surface area. Finally, compared to PODPF/PVK fibers and PODPF/PEO amorphous ES fibers, PODPF/PEO ES fibers obtained from DCE solution exhibit an excellent quenching behavior toward a saturated DNT vapor, mainly due to the synergistic effect of small size, weak separation, β-conformation formation and high deep-blue emission efficiency.

A supramolecular self-assembly material based on cucurbituril and cationic TPE as ultra-sensitive probe of energetic pentazolate salts

The successful synthesis of the pentazolate anion(cyclo-N-5)has been a great breakthrough in the field of energetic materials.However,the detection methods for these energetic materials based on the pentazolate anion are quite rare.Herein,two fluorescent probes for cyclo-N-5anion were designed.Sensor 1(TPE2N)was synthesized with a tetraphenylethylene functionalized by two cationic groups which can generate strong electrostatic interactions with pentazolate anion and result in specific fluorescent changes.Sensor 2 was designed based on sensor 1 and supramolecular cucurbit[7]uril(CB[7]).The unique structural features of CB[7]provide sites for the interaction between the cations and N-5anion in its cavity,which would generate a platform for the detection and enhance the recognition performance.Isothermal titration calorimetry(ITC)experiment and fluorescence titration experiment indicate the binding molar ratio between sensor 1 with CB[7]is 1:2.Both sensors display typical aggregation-induced emission(AIE)features and good water-solubility.The sensors demonstrate excellent sensitivity to pentazole hydrazine salt with high enhancement constant(sensor 1:1.34×10^(6);sensor 2:3.78×10^(6))and low limit of detection(LOD:sensor 1=4.33μM;sensor 2=1.54μM).The formation of an AIE-based supramolecular sensor effectively improves the sensitivity to N-5anion.In addition,the probes also have good selectivity of N-5anion salts.The research would shed some light on the design of novel fluorescent sensors to detect pentazolate-based molecules and provides an example of supramolecular chemistry combined with fluorescent probes.

Pyrrole and Pyrimidine Derivatives as Possible Electron Donors for Colored Charge-Transfer Complexes with a Weakly Electrophilic Energetic Material,FOX-7:A Theoretical Study

A number of electron-rich heterocycles are studied as potential reagents for visual colorimetric detection of FOX-7 due to colored charge-transfer complexes formation.The obtained results suggest that pyrrole and pyrimidine derivatives can form such complexes playing the role of electron donors despite a low electrophilicity of FOX-7.Density functional theory calculations,as well as quantum theory of atoms in molecules analysis,suggest stacking binding mode as the most preferable one with the binding energy of about 21-36 kJ/mol.All the complexes demonstrate a clear single charge-transfer absorption band in the visible region and the expected colors of the complexes are varying from violet and blue to red and orange.The calculations of the crystalline state of the studied complexes indicate high lattice energies,which are higher than that of pure FOX-7 and are close to the recently reported hydrogen-bonded complex of FOX-7 with 1,10-phenanthroline.Additional analysis of the studied charge-transfer complexes using properties based on density difference grids clearly suggests the acceptor role of FOX-7 in the complexes.This analysis can be effectively applied to identify the nature of other possible complexes of FOX-7,in which its role is unclear because of the specific reactivity,namely,both weak electrophilic and nucleophilic properties at the same time.

Highly Emissive Luminogens in Both Solution and Aggregate States

Organic light-emitting materials have attracted considerable attention because of their promising applications in diverse areas.Most fluorophores emit brightly in either dilute solutions or aggregate states;the former generally suffer from aggregation-caused quenching problem,and the latter encounter intensity loss at low concentrations.Herein,we propose a new strategy to overcome these dilemmas by balancing the planar and distorted structures of terphenyl-based luminogens and obtain three luminogens,2PB-AC,2Me2PB-AC,and 2T2PB-AC,with bright emission in both solution and aggregate states.Among them,2PB-AC shows absolute photoluminescence quantum yields(ФPL)higher than 90%in both tetrahydrofuran solution(90.2%)and aggregate states(92.7%for powder and 95.3%for crystal).Thus,2PB-AC could be an efficient probe to realize dual-channel explosive detection in both solution and aggregate states.Moreover,it could be used to image live-cell lipid droplets at a wide range of concentrations.In addition,benefiting from its thermodynamically favorable intersystem crossing process,2Me2PB-AC could be doped in polymethyl methacrylate matrix to provide efficient room-temperature phosphorescence.Thus,this work provides a feasible strategy for the design of luminogens with highly efficient emission in both solution and aggregate states,greatly facilitating and broadening their practical applications.

A family of oligo(p-phenylenevinylene)derivative aggregation-induced emission probes:Ultrasensitive,rapid,and anti-interfering fluorescent sensing of perchlorate via precise alkyl chain length modulation

The precise regulation of interactions provided by aggregation-induced emission(AIE)probes is of considerable significance for improving the sensing performance in the field of on-site detection.Here,a highly sensitive perchlorate detection probe was designed by precisely modulating the van der Waals interactions by adjusting the length of the alkyl chain.The optimized AIE probe demonstrated superior perchlorate detection performance owing to its strong van der Waals interactions with perchlorate,including a low detection limit(53.81 nM),rapid response(<5 s),and excellent specificity even in the presence of 16 interfering anions.In addition,a hydrogel-based device loaded with the probe was constructed to achieve ultrasensitive recognition of perchlorate particles with a detection limit as low as 15 fg under a fluorescence microscope.Moreover,the practicality of the probe was further verified by employing a sensing chip in a portable detector,and thus the probe has been proven to be highly promising for trace perchlorate monitoring in real scenarios.We expect the present study to be of great value for the efficient design of high-performance fluorescent probes.

Synthesis of Functional Hyperbranched Poly(methyltriazolylcarboxylate)s by Catalyst-free Click Polymerization of Butynoates and Azides

Azide-alkyne click polymerization has become a powerful tool for polymer synthesis.However,the click polymerization between internal alkynes and azides is rarely utilized to prepare functional polymers.In this work,the polymerization reactions of activated internal alkyne monomers of tris(2-butynoate)s(1)with tetraphenylethene-containing diazides(2)were performed in dimethylformamide(DMF)under simple heating,affording four hyperbranched poly(methyltriazolylcarboxylate)s(hb-PMTCs)with high molecular weights(A4W up to 2.4 x 104)and regioregularities(up to 83.9%)in good yields.The hb-PMTCs are soluble in common organic solvents,and thermally stable with 5%weight loss temperatures up to 400℃.They are non-emissive in dilute solution,but become highly emissive in aggregated state,exhibiting aggregationinduced emission characteristics.The polymers can generate fluorescent photopatterns with high resolution,and can work as fluorescent sensors to detect nitroaromatic explosive with high sensitivity.

Direct identification of HMX via guest-induced fluorescence turn-on of molecular cage

Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine(HMX) is one of the most widely used powerful explosives. The direct and selective detection of HMX, without the requirement of specialized equipment, remains a great challenge due to its extremely low volatility, unfavorable reduction potential and lack of aromatic rings. Here, we report the first chemical probe of direct identification of HMX at ppb sensitivity based on a designed metal-organic cage(MOC). The cage features two unsaturated dicopper units and four electron donating amino groups inside the cavity, providing multiple binding sites to selectively enhance host-guest events. It was found that compared to other explosive molecules the capture of HMX inside the cavity would strongly modulate the emissive behavior of the host cage, resulting in highly induced fluorescence “turn-on”(160 folds). Based on the density functional theory(DFT) simulation, the mutual fit of both size and binding sites between host and guest leads to the synergistic effects that perturb the ligand-to-metal charge-transfer(LMCT) process, which is probably the origin of such selective HMX-induced turn-on behavior.