Antenna-based optimization of triplet radioluminescence of Tb-organic complex scintillator for efficient X-ray detection.

Triplet exciton is both a luminescence quenching factor and an important luminescence sensitization technology solution, which is widely concerned in the field of optoelectronic materials. Since X-ray excited triplet excitons are dissipated through various pathways, there are still huge difficulties in achieving efficient triplet sensitized emission. Here, the antenna ligand is regulated through the carboxyl group, increasing the steric hindrance between the conjugated groups and improving triplet-enhanced radioluminescence (RL) efficiencies of Tb3+. The lanthanide metal-organic frameworks (Ln-MOFs) formed by the coordination of Tb3+ with mellitic acid (MA), pyromellitic acid (PMA) and trimesic acid (TMA) under low temperature preparation conditions. Among them, MA-Tb has a longer spacing between conjugated groups than PMA-Tb and TMA-Tb, and its triplet RL is relatively strongest, with a light yield of 28,000 photons MeV-1. Mechanistic studies revealed that the RL efficiency of Ln-MOFs is related to the π-π stacking effect in the benzene ring. In addition, the application of MA-Tb in the field of X-ray detection was demonstrated. The RL intensity of MA-Tb has a good linear relationship with the X-ray dose rate, and the detection limit for X-ray reaches 82 nGy/s, which is 66 times lower than the typical medical imaging dose. These results will provide a universal strategy for the design of Ln-MOFs scintillator.

Modulating the D-π-A Interactions in Metal-Covalent Organic Frameworks for Efficient Electroreduction of CO2 into Formate.

Crystalline porous framework materials have attracted tremendous interest in electrocatalytic CO2 reduction owing to their ordered structures and high specific surface areas as well as rich designability, however, still suffer from a lack of accuracy in regulating the binding strength between the catalytic sites and intermediates, which is crucial for optimizing the electrocatalytic activity and expanding the product types. Herein, we report three new kinds of vinylene-linked metal-covalent organic frameworks (TMT-CH3-MCOF, TMP-CH3-MCOF and TMP-MCOF) with continuously tunable D-π-A interactions by adjusting the structure of the monomers at the molecular level for realizing efficient electroreduction of CO2 to formate for the first time. Interestingly, compared with TMT-CH3-MCOF and TMP-MCOF, the TMP-CH3-MCOF exhibited the highest HCOO- Faradaic efficiency (FEHCOO-) of 95.6 % at -1.0 V vs RHE and displayed the FEHCOO- above 90 % at the voltage range of -1.0 to -1.2 V vs. RHE, which is one of the highest among various kinds of reported electrocatalysts. Theoretical calculations further reveal that the catalytic sites in TMP-CH3-MCOF with unique moderate D-π-A interactions have suitable binding ability towards the reaction intermediate, which is beneficial for the formation of *HCOO and desorption of *HCOOH, thus effectively promoting the electroreduction of CO2 to formate.

High-throughput fluorescence sensing array based on tetraphenylethylene derivatives for detecting and distinguishing pathogenic microbes.

Infections induced by pathogenic microorganisms will bring negative effects such as diseases that damage health and result in heavy economic burden. Therefore, it is very important to detect and identify the pathogens in time. Moreover, traditional clinical diagnosis or food testing often faces the problem of dealing with a large number of samples. Here, we designed a high-throughput fluorescent sensor array based on the different binding ability of five tetraphenylethylene derivatives (TPEs) with various side chains to different kinds of pathogenic microbes, which is used to detect and distinguish various species, so as to realize rapid mass diagnosis, and hopefully provide guidance for further determination of microbial infections and clinical treatment.

Fully Conjugated 2D sp2 Carbon-Linked Covalent Organic Frameworks for Photocatalytic Overall Water Splitting.

Covalent organic frameworks (COFs) hold great promise for solar-driven hydrogen production. However, metal-free COFs for photocatalytic overall water splitting remain elusive, primarily due to challenges in simultaneously regulating their band structures and catalytic sites to enable concurrent half-reactions. Herein, two types of π-conjugated COFs containing the same donor-acceptor structure are constructed via Knoevenagel condensation and Schiff base reaction to afford cyanovinylene- and imine-bridged COFs, respectively. The difference in the linkage leads to a remarkable difference in their photocatalytic activity toward water splitting. The 2D sp2 carbon-linked COF exhibits notable activity for photocatalytic overall water splitting, which can reach an apparent quantum efficiency of 2.53% at 420 nm. In contrast, the 2D imine-linked COF cannot catalyze the overall water-splitting reaction. Mechanistic investigations reveal that the cyanovinylene linkage is essential in modulating the band structure and promoting charge separation in COFs, thereby enabling overall water splitting. Moreover, it is further shown that crystallinity substantially impacts the photocatalytic performance of COFs. This study represents the first successful example of developing metal-free COFs with high crystallinity for photocatalytic overall water splitting.

Preparation and p-phenylenediamine detection mechanism of a dialdehyde cellulose and a 7-amino-4-methylcoumarin-based fluorescent probe.

A novel fluorescent probe, fluorescent dialdehyde cellulose (FDAC), was prepared to detect p-phenylenediamine (PPD) in water samples conveniently and quickly. This was achieved by grafting 7-amino-4-methylcoumarin (AMC) onto dialdehyde cellulose (DAC) via an aldol-amine condensation reaction. This method is greener, more economical, and simpler than existing methods for preparing fluorescent probes. The probe was found to be more effective for PPD detection in polar solvents, with less interference from pH and other compounds present in the sample matrix. The photoluminescence of FDAC at λex/λem = 340/430 nm was statically quenched by PPD, allowing for accurate detection within the range of 10-100 µmol/L under optimal conditions, with a detection limit of 3.2 µmol/L (3 σ/s). Meanwhile, the Schiff base (-C=N- group) generated by the condensation of DAC and AMC increased the reaction activity of the fluorescent moiety and changed the AMC conjugated structure, making FDAC more susceptible to aminolysis with PPD than AMC. This study presents a promising solution for fluorescence detection of aniline compounds, with significant potential for application in fields such as environmental analysis.

Fully-Conjugated Covalent Organic Frameworks with Two Metal Sites for Oxygen Electrocatalysis and Zn-Air Battery.

Covalent organic frameworks (COFs) are a promising alternative toward catalysis, due to the unique framework structure and the excellent chemical stability. However, the scarcity of unsaturated metal sites and the low conductivity have constrained the advancement of these materials for catalysis of electrochemical reactions. Exploring next-generation conductive metal-covalent organic frameworks (M-COFs) with extra metal active sites is crucial for improving their catalytic activity. Herein, a novel fully-conjugated M-COFs (Co-PorBpy-Co) with two types of metal sites is proposed and achieved by solvothermal method in the presence of carbon nanotube (CNT). The electrocatalyst constructed by the Co-PorBpy-Co exhibits excellent oxygen reduction reaction (ORR) activity (E1/2 = 0.84 V vs RHE, n = 3.86), superior to most COFs-based catalysts. Theoretical result shows the CoN2 sites are extremely active for ORR, and Co-PorBpy-Co exhibits excellent conductivity for electron transfer. The Zn-air battery constructed by Co-PorBpy-Co/CNT manifests excellent power density (159.4 mW cm-2 ) and great cycling stability, surpassing that of 20 wt% Pt/C catalyst. This work not only proposes a novel design concept for electrocatalysts, but establishes a mechanism platform for single-metal atom electrocatalysis and synergistic effect.

Natural xylose-derived carbon dots towards efficient semi-artificial photosynthesis.

Photosynthesis by plants stores sunlight into chemicals and drives CO2 fixation into sugars with low biomass conversion efficiency due to the unoptimized solar spectrum utilization and various chemical conversion possibilities that follow H2O oxidation. Expanding the solar spectrum utilization and optimizing the charge transfer pathway of photosynthesis is critical to improving the conversion efficiency. Here, a group of carbon dots (CDs) with distinct content of sp2 CC domain are prepared by one-step carbonization of natural xylose, which penetrated natural chloroplasts and integrated with the grana thylakoid to promote in vitro photosynthesis. Structural characterization and electrochemical results reveal the positive impact of graphitization degree on the electron transport capacity of CDs. Classic Hill reaction and ATP production demonstrate the enhanced photosynthetic activity resulting from the CDs-mediated electron transfer of photosystem II. In-depth studies of the structure-function relationship prove the synergistic effect of intensified biotic-abiotic interaction between CDs and chloroplast, lower charge transfer resistance, and extended light absorption. This work posts a promising method to optimize electron transport and improve natural photosynthesis using artificial interventions.

K3C6N7O3·2H2O: A Multifunctional Nonlinear Optical Cyamelurate Crystal with Colossal π-Conjugated Orbitals.

The delocalized π-conjugated units are considered as an advantageous gene for improving the optical nonlinearity of acentric crystals. For the first time, we synthesized a new acentric SHG-active metal cyamelurate crystal K3C6N7O3·2H2O (I) by a facile solution method, containing a colossal planar π-conjugated (C6N7O3)3- unit. It displays a strong second-order harmonic generation (SHG) of 4 × KDP and a giant anisotropic birefringence of 0.446 at 1064 nm. The theoretical calculations reveal that such substantial improvement is contributed from the strong molecular susceptibility of (C6N7O3)3- units and their near-perfect coplanar arrangement. Moreover, I exhibits a broadband ultraviolet photoluminescence at 366 nm, suggesting its multifunctional capacity and great potential for compact highly integrated optoelectronic devices.

Carbon Nitride with Rationally Designed π-Conjugated Structure for Bright Blue-Violet Light-Emitting Diodes.

Carbon nitride consisting of the broken π-conjugated structure (bc-CN) is designed as the emitting layer in a blue-violet light emitting diode (LED). The bc-CN is prepared by a metal-oxide (MgO) template-assisted method, in which the low reaction temperature and nano MgO jointly control the degree of polymerization to form cyano groups and broken π-conjugation in the bc-CN nanosheets (bc-CN NS) which emit intense blue-violet photoluminescence at 412 nm. The broken π-conjugated heptazine-ring structure in the bc-CN NS mitigates non-radiation energy loss and promotes the d*-LP transition. As a result, a high quantum efficiency of 73.1% is achieved. The excellent dispersing ability of the bc-CN NS enables solution-based fabrication of the light emitting diode (LED). The LED exhibits intense electroluminescence of 236 cd m-2 at 412 nm with an external quantum efficiency of 0.46%. The broken π-conjugation modulates the optical properties of the polymerized carbon nitride semiconductor giving rise to intense blue-violet electroluminescence, which is very desirable for printable and wide-color-gamut display devices.

Flame Retardancy Properties and Rheological Behavior of PP/DiDOPO Conjugated Flame Retardant Composites.

A bridged 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative (DiDOPO) with conjugated structure was utilized as a novel conjugated flame retardant, Polypropylene(PP)/DiDOPO conjugated flame retardant composites were papered by being melt-extruding with a twin-screw extruder. The flame retardant efficiency of PP/DiDOPO conjugated flame retardant composites were investigated by cone calorimetry, limiting oxygen index (LOI), vertical burning test (UL-94). Besides, the rheological behavior of PP/DiDOPO conjugated flame retardant composites are measured by ARES rheometer. The results showed that when the content of DiDOPO with conjugated structure was 16 wt%, the LOI values of PP/DiDOPO conjugated flame retardant composites was 24%, and PP/DiDOPO conjugated flame retardant composites reaches V-0 grade. The heat release rate (HRR), total heat release rate (THR) and CO2 of PP/DiDOPO conjugated flame retardant composites decreased, so PP/DiDOPO conjugated flame retardant composites had excellent flame retardant effect. Rheological analysis results indicated that DiDOPO with conjugated structure suppressed the melt dripping of PP/DiDOPO conjugated flame retardant composites by enhancing the melt stability. The results showed that the DiDOPO with conjugated structure can significantly enhance the flame retardancy effect of PP/DiDOPO conjugated flame retardant composites. In addition, the materials PP/DiDOPO might be with low conductivity and charge transport mobility.

Synchronous construction of a porous intramolecular D-A conjugated polymer via electron donors for superior photocatalytic decontamination.

The development of conjugated polymers with intramolecular donor-acceptor (D-A) units has the capacity to enhance the photocatalytic performance of carbon nitride (g-C3N4) for the removal of antibiotics from ambient ecosystems. This strategy addresses the challenge of narrowing the band gap of g-C3N4 while maintaining its high LUMO position. For this study, we introduced the above donor units into g-C3N4 to construct intramolecular D-A structures through the copolymerization of dicyandiamide with creatinine, which strategically extended light absorption into the green region and expedited photoelectron separation. The introduction of electron donor blocks kept the LUMO distributed on the melem, which maintained the high LUMO energy level of the copolymer with the potential to generate oxygen radicals. The as-prepared porous D-A conjugated polymer enhanced the photocatalytic degradation of sulfisoxazole with kinetic constants 5.6 times higher than that of g-C3N4 under blue light and 15.3 times higher under green light. Furthermore, we surveyed the degradation mechanism including the effective active species and degradation pathways. This study offers a new perspective for the synchronous construction of a porous intramolecular D-A conjugated polymer to enhance water treatment and environmental remediation capacities.

Low-Permittivity Copolymerized Polyimides with Fluorene Rigid Conjugated Structure.

As the miniaturization of electronic appliances and microprocessors progresses, low-permittivity interlayer materials are becoming increasingly important for their suppression of electronic crosstalk, signal propagation delay and loss, and so forth. Herein, a kind of copolyimide (CPI) film with a "fluorene" rigid conjugated structure was prepared successfully. By introducing 9,9-Bis(3-fluoro-4-aminophenyl) fluorene as the rigid conjugated structure monomer, a series of CPI films with different molecular weights were fabricated by in situ polymerization, which not only achieved the reduction of permittivity but also maintained excellent thermodynamic stability. Moreover, the hydrophobicity of the CPI film was also improved with the increasing conjugated structure fraction. The lowest permittivity reached 2.53 at 106 Hz, while the thermal decomposition temperature (Td5%) was up to 530 °C, and the tensile strength was ≥ 96 MPa. Thus, the CPI films are potential dielectric materials for microelectronic and insulation applications.

Interfacial Engineering of Hybrid Polydopamine/Polypyrrole Nanosheets with Narrow Band Gaps for Fluorescence Sensing of MicroRNA.

Nanoquencher-based biosensors have emerged as powerful tools for the detection of tumor markers, where challenges in efficiently docking the π-electron interaction interface toward nucleic acid probes containing π-electron-rich units of bases and fluorescent dyes still remain. Herein, we present hybrid polydopamine/polypyrrole nanosheets (PDA-PPy-NS) with π electron coupling and ultranarrow band gap (0.29 eV) by interfacial engineering of polymer hybrids at the nanoscale. PDA-PPy-NS were first prepared through oxidant-induced polymerization of pyrrole on PDA nanosheets. By utilizing fluorescent-dye-labeled single-stranded DNA as a probe, the hybrid nanoquencher showed ultrahigh fluorescence quenching ability, i.e., a Cy5-ssDNA/nanoquencher mass ratio of 36.9 under the complete quenching condition, which is comparable to that of graphene oxide. It was demonstrated that the energy level coupling of nanosheets and nucleic acid dye (Cy5) was the key factor contributing to the efficient photoinduced electron transfer (PET). Subsequently, the nanoquencher/DNA probe was proved to possess superior sensitivity and selectivity for efficient and reliable detection of miRNA-21 with a detection limit of 23.1 pM. Our work proves that the π-electron-rich biosensor interface can significantly enhance the PET efficiency, providing a theoretical basis for developing novel high-performance sensors.

Photoluminescence with an unusual open-loop and rigid delocalized conjugated structure in quantum dots.

It is well known that almost all photoluminescent molecules are aromatic or heterocyclic ring compounds for bioimaging analysis. A question remains as to whether a breakthrough can be achieved regarding a novel photoluminescent molecule without a ring structure, and in a what manner. In this study, we explored the photoelectric conversion and structure of photoluminescent compounds, and constructed an intra-molecular coupling positive-negative-junction (PNJ) with an open-loop and rigid Π56 delocalized conjugated structure of the coupling p-π conjugate system. This was performed to enable strong absorption of the R/tail-end band for the high probability of an n â†’ π*/n â†’ σ* electron transition for photoluminescence production. Subsequently, the Π56 structure was formed in a short-chain aliphatic molecule as a hydrolytic product of citric acid and urea, and computational methodology was employed to estimate the feasibility of the molecule photoluminescence. Finally, a quantum dot material was fabricated from the aliphatic molecule, the optical properties of the quantum dots were investigated, and the biocompatibility and bioimaging ability of quantum dots were assessed. This work presents not only a theoretical exploration but also practical application of a new strategy to obtain molecules, compounds, and materials with bioimaging.

Formation and Evolution of sp2 Hybrid Conjugate Structure of Polyacrylonitrile Precursor during Stabilization.

The generated sp2 hybrid conjugate structure of a C atom, which resulted from the chemical reaction affected by temperature and time, is an effective six-membered ring planar structure of the final carbon fiber. This kind of hybrid conjugate structure determined the formation of the final structure and mechanical properties of carbon fiber. In this paper, the formation and evolution of sp2 hybrid conjugated structures of PAN precursor during thermal stabilization were investigated by Raman, UV-vis and 13C-NMR methods. The results indicated that with the increase of stabilization temperature, the degree of the sp2 hybrid conjugated structure of stabilized PAN fiber increases "linearly", while the content of the sp2 hybrid carbon atoms increases with "S-type". The final sp2 hybrid conjugated ring structure is mainly composed of single-ring, double-ring, triple-ring, and double-bond structures. Compared with the time factor, the temperature effect plays a decisive role in the formation of the sp2 hybrid conjugate structure.

Design, synthesis and biological evaluation of novel neuchromenin analogues as potential antifungal agents.

In continuation of our program to discover new potential antifungal agents, thirty-two neuchromenin analogues were synthesized and characterized by the spectroscopic analysis. By using the mycelium growth rate method, the target compounds were evaluated systematically for antifungal activities in vitro against six plant pathogenic fungi, and structure-activity relationships (SAR) were derived. Compounds 6b-c, and 6l showed obvious inhibition activity on each of the fungi at 50 µg/mL. For the corresponding fungi, 7 of the compounds showed average inhibition rates of >80% at 50 µg/mL; especially, compounds 6b, 6d-e, and 6i-l displayed more potent antifungal activity against A. solani than that of thiabendazole (a positive control). Moreover, compound 6c also exhibited good activity against C. lunata with EC50 values of 12.7 µg/mL, and the value was much superior to that of thiabendazole (EC50 = 59.7 µg/mL). SAR analysis showed that the presence of conjugated structure, bearing a C=C bond conjugated to the C=O group, obviously decreased the activity; the type and position of the substituted R5 significantly influenced the activity. Furthermore, the significantly bioactive compounds 6b-e, 6g, 6i and 6l showed very low toxicities against HL-7702, BEL-7402 and HCT-8 cells. Resistance development assay indicated that compounds 6b-e and 6l failed to induce the two tested strains of fungi to develop resistance. SEM analysis initially revealed that compound 6d may exert its antifungal effect by damaging fungal cell wall.

Coordination-driven synthesis of perfected π-conjugated graphitic carbon nitride with efficient charge transfer for oxygen activation and gas purification.

Efficient yield of reactive-oxygen species (ROS) is greatly important for environmental purification and engineering. In this study, the perfected π-conjugated g-C3N4 (PNa-g-C3N4) photocatalysts were constructed by coordination between 3p orbits of Na and N 2p lone electron at vacancy structure of tri-s-triazine polymer for ROS evolution and elimination of HCHO and NO. The perfected π-conjugated structure enhances the visible-light capturing capability, enriches active sites for O2 activation, and promotes the directional charge transfer from N 2p of C3-N to Na and C. Therefore, the superior activities including the evolution of O2- (35 µmol.L-1h-1), and H2O2 (517 µmol.L-1h-1) have been achieved over PNa-g-C3N4 photocatalyst. As a result, PNa-g-C3N4 photocatalysts demonstrate high performances removal efficiency of NO (53% for 6 min), and HCHO (almost 100% for 55 min) in the elimination process. The results may provide the promising strategy to construct efficient photocatalytic system to yield ROS for environmental purification.

Conjugation in multi-tetrazole derivatives: a new design direction for energetic materials.

Multi-tetrazole derivatives with conjugated structures were designed and investigated in this study. Using quantum chemistry methods, the crystal structures, electrostatic potentials (ESPs), multicenter bond orders, HOMO-LUMO energy gaps, and detonation properties of the derivatives were calculated. As expected, these molecules with conjugated structures showed low energies of their crystal structures, molecular layering in their crystals, high average ESPs, high multicenter bond order values, and enhanced detonation properties. The derivative 1,2-di(1H-tetrazol-5-yl)diazene (N2) was predicted to have the best density (1.87 g/cm3), detonation velocity (9006 m/s), and detonation pressure (36.8 GPa) of the designed molecules, while its total crystal energy was low, suggesting that it is relatively stable. Its sensitivity was also low, as the molecular stacking that occurs in its crystal allows external forces to be dissipated into movements of crystal layers. Finally, its multicenter bond order was high, indicating a highly conjugated structure.