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Matrix Effect on Polydiarylfluorenes Electrospun Hybrid Microfibers: From Morphology Tuning to High explosive detection Efficiency

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Chinese Journal of Polymer Science 2023年第7期41卷 1011-1017页

作者： Wei Xue Man Xu Chuan-Xin Wei Hua-Min Sun Li-Li Sun Sheng-Jie Wang Jin-Yi Lin Nai-En Shi Ling-Hai Xie Wei Huang State Key Laboratory of Organic Electronics and Information Displays&Institute of Advanced Materials(IAM) Nanjing University of Posts&TelecommunicationsNanjing210023China Center for Supramolecular Optoelectronics(CSO) Key Laboratory of Flexible Electronics(KLOFE)and Institute of Advanced Materials(IAM)Nanjing Tech University(NanjingTech)Nanjing211816China Frontiers Science Center for Flexible Electronics(FSCFE) Shaanxi Institute of Flexible Electronics(SIFE)&Shaanxi Institute of Biomedical Materials and Engineering(SIBME)Northwestern Polytechnical University(NPU)Xi’an710072China

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.

关键词： Matrix effect Electrospun fibers Polydiarylfluorenes Planar conformation explosive detection

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Cooperative Supramolecular Polymerization of Propeller-Shaped Triphenylamine Cyanostilbenes for explosive detection

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Chinese Journal of Polymer Science 2023年第4期41卷 585-592,I0009页

作者： Long-Yu Guang Zhi-Feng Zhou Yi-Fei Zhang Lai-Wei Gao Feng Wang Rui Liao CAS Key Laboratory of Soft Matter Chemistry Department of Polymer Science and EngineeringUniversity of Science and Technology of ChinaHefei230026China Clinical Laboratory The Second People’s Hospital of HefeiHefei230011China

Self-assembly ofπ-conjugated compounds into supramolecular polymers has received considerable attention because of their intrinsic scientific interests and technological *** compared toπ-conjugated rods,discotics,and macrocycles,propeller-shapedπ-conjugated molecules have been less exploited to form long-range-ordered supramolecular *** a novel type of supramolecular polymers has been constructed on the basis of propeller-shaped triphenylamine *** designed compound adopts nucleation-elongation cooperative mechanism for the supramolecular polymerization process,because of the participation of three-fold hydrogen bonds between the neighbouring *** supramolecular polymeric state displays amplified chirality and enhanced emission than those in the monomeric *** 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 *** 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.

关键词： Supramolecular polymers D-π-A molecules Supramolecular chirality Fluorescence explosive detection

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Tetraphenylpyrimidine-based AIEgens with Potential for explosive detection

Tetraphenylpyrimidine-based AIEgens with Potential for Explo...

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第十三届全国量子化学会议

作者： Junkai Liu Key Laboratory of Organic solids Beijing National Laboratory for Molecular Sciences (BNLMS) Institute of Chemistry Chinese Academy of Sciences

A new type of AIEgen derived from Tetraphenylpyrimidine（TPPM） were rationally designed according to the RIR mechanism and synthesized through the efficient way. Geometrical optimization for TPPM derivatives indicated that changes in bond angles of the pyrimidine ring contribute large proportion of reorganization energy. Symmetrical substituents of TPPM with electron-donating groups could constrain the intense breathing motion of the central pyrimidine ring, suppressing the non-radiative decay process and promoting emission efficiency in the solution. Furthermore, intensified emission in the aggregates and large spectra overlap combined with H-bond enhanced electron transformation endow TPPM-AIEgens with high performance for explosive detection.

关键词： Tetraphenylpyrimidine Aggregation-induced emission explosive detection

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

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Chinese Journal of Polymer Science 2020年第11期38卷 1171-1177,I0005页

作者： Mu-Ning Lang Wei-Wen Chi Ting Han Qing-Zhen Zhao Hong-Kun Li Ben Zhong Tang Yong-Fang Li State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials Laboratory of Advanced Optoelectronic MaterialsCollege of ChemistryChemical Engineering and Materials ScienceSoochow UniversitySuzhou 215123China State Key Laboratory of Luminescent Materials and Devices Key Laboratory of Luminescence from Molecular Aggregates of Guangdong ProvinceCenter for Aggregation-Induced EmissionSouth China University of TechnologyGuangzhou 510640China Department of Chemistry Hong Kong Branch of Chinese National Engineering Research Center for Tissue Restoration and ReconstructionThe Hong Kong University of Science&TechnologyClear Water BayKowloonHong KongChina

Azide-alkyne click polymerization has become a powerful tool for polymer ***,the click polymerization between internal alkynes and azides is rarely utilized to prepare functional *** 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 *** 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 *** polymers can generate fluorescent photopatterns with high resolution,and can work as fluorescent sensors to detect nitroaromatic explosive with high sensitivity.

关键词： Click polymerization Hyperbranched polymer Aggregation-induced emission explosive detection Photopattern

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

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Chinese Chemical Letters 2021年第12期32卷 4006-4010页

作者： Chen Wang Jin Shang Li Tian Hongwei Zhao Peng Wang Kai Feng Guokang He Jefferson Zhe Liu Wei Zhu Guangtao Li Department of Chemistry Tsinghua UniversityBeijing 100084China School of Energy and Environment City University of Hong KongHong KongChina Department of Mechanical Engineering The University of MelbourneParkvilleVIC 3010Australia School of Biology and Biological Engineering South China University of TechnologyGuangzhou 510006China Institute of chemistry Hebrew University of JerusalemJerusalem 91904Israel

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.

关键词： Chemical sensing explosive detection HMX Molecular cage Host-guest chemistry Fluorescence turn-on

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Optical sensing of explosives in wastewater by competitive complexation

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Progress in Natural Science:Materials International 2019年第6期29卷 655-659页

作者： Jiaxin Niu Hong Chi Pingxin Gao Zongkuan Liu Xiaohu Yin Zhaolin Gu School of Human Settlement and Civil Engineering Xi'an Jiaotong University Shandong Provincial Key Laboratory of Molecular Engineering School of Chemistry and Pharmaceutical Engineering Qilu University of Technology (Shandong Academy of Sciences)

A facile strategy for optical sensing of explosives with the assistance of 1,3,5-Triazine-2,4,6-triamine（MEL） in aqueous solution is proposed. Upon exposure to MEL, the electron-sufficient amino group in MEL was prone to form complexes with electron-deficient nitro group in explosives. The interaction could be tuned by the amount of MEL to fully consumed nitro-contained explosives dissolved in wastewater, thus prevented the gold nanoparticles（GNPs） from combining with MEL. In comparison with common detection method, the dose-response curve procedure reported here was in good linear relationship from 0 μM to 80 μM with good correlation factor（R;= 0.9871）, and was satisfactorily agreed with the proposed theoretical model. The detection limit（Lo D） was1.1 μM by spectrometer, 3.0 μM visualized by naked eyes and 21.3 nM by calculation. The procedure described in this study could be finished within a few minutes and showed its effectiveness in explosive detection upright on the gold surface in real wastewater, making this proposed method a powerful tool in several sensing platforms.

关键词： explosive detection Optical sensing Competitive complexation Gold nanoparticles 1,3,5-Triazine-2,4,6-triamine

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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

Aggregate

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Aggregate 2023年第2期4卷 183-192页

作者： Fangfang Xiao Yushu Li Jiguang Li Da Lei Guangfa Wang Tianshi Zhang Xiaoyun Hu Xincun Dou Xinjiang Key Laboratory of explosives Safety Science Xinjiang Technical Institute of Physics&ChemistryChinese Academy of SciencesUrumqiChina Center of Materials Science and Optoelectronics Engineering University of Chinese Academy of SciencesBeijingChina

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 ***,a highly sensitive perchlorate detection probe was designed by precisely modulating the van der Waals interactions by adjusting the length of the alkyl *** 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(detection limit as low as 15 fg under a fluorescence ***,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 *** expect the present study to be of great value for the efficient design of high-performance fluorescent probes.

关键词： aggregation-induced emission explosive detection fluorescent probe perchlorate trace sensing

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Highly Emissive Luminogens in Both Solution and Aggregate States

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CCS Chemistry 2023年第7期5卷 1686-1696页

作者： Pengbo Han Guiquan Zhang Jia Wang Yejun Yao Yanping Qiu He Xu Anjun Qin Ben Zhong Tang State Key Laboratory of Luminescent Materials and Devices Guangdong Provincial Key Laboratory of Luminescence from Molecular AggregatesSouth China University of TechnologyGuangzhou 510640 Center for Aggregation-Induced Emission AIE InstituteSouth China University of TechnologyGuangzhou 510640 School of Science and Engineering Shenzhen Institute of Aggregate Science and TechnologyThe Chinese University of Hong KongShenzhen 518172 Hong Kong Branch of Chinese National Engineering Research Centre for Tissue Restoration and Reconstruction The Hong Kong University of Science&TechnologyClear Water BayKowloonHong Kong 999077China

Organic light-emitting materials have attracted considerable attention because of their promising applications in diverse *** 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 ***,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 *** 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 ***,it could be used to image live-cell lipid droplets at a wide range of *** addition,benefiting from its thermodynamically favorable intersystem crossing process,2Me2PB-AC could be doped in polymethyl methacrylate matrix to provide efficient room-temperature ***,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.

关键词： highly emissive luminogens roomtemperature phosphorescence explosive detection lipid droplets

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Study on Source Neutron Moderation of PFTNA Landmine detection

Study on Source Neutron Moderation of PFTNA Landmine Detecti...

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第三届全国核技术与应用学术研讨会

作者： G.Ding,F.H.Hao,C.S.Chu~*,J.Zeng,Q.P.Xiang,J.R.Lei,G.C.Hu Institute of Nuclear Physics and Chemistry,China Academy of Engineering Physics,Mianyang 621900,China

For higher detection speed of N,H elements in the pulsed fast/thermal neutron analysis("PFTNA"for short) landmine detection experiment,a brand new moderator designed by Mont-Carlo method was introduced to the pulsed d-T neutron *** calculation result was validated by experiments,and the verification result indicates that,the adoption of graphite moderator can not only largely improvethe detection speed of N,H elements,but also enhance the measurement of C,O by increasing the fast neutron flux.

关键词： pulsed fast/thermal neutron PFTNA landmine detection explosive detection M-C simulation

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