Integrating Time-Resolved Imaging Information by Single-Luminophore Dual Thermally Activated Delayed Fluorescence

The fact that the lifetime of photoluminescence is often difficult to access because of the weakness of the emission signals, seriously limits the possibility to gain local bioimaging information in time-resolved luminescence probing. We aim to provide a solution to this problem by creating a general photophysical strategy based on the use of molecular probes designed for single-luminophore dual thermally activated delayed fluorescence (TADF). The structural and conformational design makes the dual TADF strong in both diluted solution and in an aggregated state, thereby reducing sensitivity to oxygen quenching and enabling a unique dual-channel time-resolved imaging capability. As the two TADF signals show mutual complementarity during probing, a dual-channel means that lifetime mapping is established to reduce the time-resolved imaging distortion by 30–40 %. Consequently, the leading intracellular local imaging information is serialized and integrated, which allows comparison to any single time-resolved signal, and leads to a significant improvement of the probing capacity.     

Precisely Controlled Multidimensional Covalent Frameworks: Polymerization of Supramolecular Colloids

Rapid and selective removal of micropollutants from water is important for the reuse of water resources. Despite hollow frameworks with specific functionalized porous walls for the selective adsorption based on a series of interactions, tailoring a stable shape of nanometer- and micrometer-sized architectures for the removal of specific pollutants remains a challenge. Here, exactly controlled sheets, tubes, and spherical frameworks were presented from the crosslinking of supramolecular colloids in polar solvents. The frameworks strongly depended on the architecture of original supramolecular colloids. As the entropy of colloids increased, the initial laminar framework rolled up into hollow tubules, and then further curled into hollow spheres. These shape-persistent frameworks showed unprecedented selectivity as well as specific recognition for the shape of pollutants, thus contributing to efficient pollutant separation.     

Heteroleptic [Cu(NN)P2]+-type cuprous complexes and their structural modulation on phosphorescent color: Synthesis,structural characterization,properties, and theoretical calculations

Four new heteroleptic [Cu(NN)P₂]⁺-type cuprous complexes— 1 -TPP, 2 -POP, 3 -Xantphos, and 4 -DPPF—were designed and synthesized using a diimine ligand 2-(2′-pyridyl)benzoxazole (2-PBO) and different phosphine ligands (TPP, triphenylphosphine; POP, bis[2-(diphenylphosphino)phenyl]ether; Xantphos, 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; DPPF, 1,1′-bis(diphenylphosphino)-ferrocene). All complexes were characterized using single-crystal X-ray diffraction, spectroscopic analysis (infrared, UV–Vis.), elemental analysis, and photoluminescence (PL). Single-crystal X-ray diffraction revealed complexes 1 – 4 as isolated cation complex structures with a tetrahedral CuN₂P₂ coordination geometry and diverse P–Cu–P angles. Their UV–Vis. absorption spectra exhibited a blue-shift sequence in wavelength with an enlarged P–Cu–P angle from 4 to 2 then to 3 and then to 1 . The PL emission peaks of 1 – 3 also exhibited a similar blue-shift sequence ( 2 → 3 → 1 ). Their PL lifetime in microseconds (~7.5, 5.1, and 4.7 μs for 1 , 2 , and 3 , respectively) indicated that their PL behavior represents phosphorescence. Time-dependent density functional theory (TD-DFT) calculation and wavefunction analysis revealed that S₁ and T₁ states of 1 – 3 should be assigned as metal–ligand and ligand–ligand charge-transfer (ML + L'L)CT states. Their UV–Vis. absorption and phosphorescence should be attributed to the charge transfer from the P–Cu–P segment to the 2-PBO ligand. Therefore, as the P–Cu–P angle increased (lower HOMO), the energy of S₁ and T₁ states also increased, following the change of PL color.     

A [001]-Oriented Hittorf's Phosphorus Nanorods/Polymeric Carbon Nitride Heterostructure for Boosting Wide-Spectrum-Responsive Photocatalytic Hydrogen Evolution from Pure Water

Red phosphorus is a promising photocatalyst with wide visible-light absorption up to 700 nm, but the fast charge recombination limits its photocatalytic hydrogen evolution reaction (HER) activity. Now, [001]-oriented Hittorf's phosphorus (HP) nanorods were successfully grown on polymeric carbon nitride (PCN) by a chemical vapor deposition strategy. Compared with the bare PCN and HP, the optimized PCN@HP hybrid exhibited a significantly enhanced photocatalytic activity, with HER rates reaching 33.2 and 17.5 μmol h⁻¹ from pure water under simulated solar light and visible light irradiation, respectively. It was theoretically and experimentally indicated that the strong electronic coupling between PCN and [001]-oriented HP nanorods gave rise to the enhanced visible light absorption and the greatly accelerated photoinduced electron–hole separation and transfer, which benefited the photocatalytic HER performance.     

Polypyridine-Based Helical Amide Foldamer Channels: Rapid Transport of Water and Protons with High Ion Rejection

Synthetic strategies that enable rapid construction of covalent organic nanotubes with an angstrom-scale tubular pore remain scarcely reported. Reported here is a remarkably simple and mild one-pot polymerization protocol, employing POCl₃ as the polymerization agent. This protocol efficiently generates polypyridine amide foldamer-based covalent organic nanotubes with a 2.8 nm length at a yield of 50 %. Trapping single-file water chains in the 2.8 Å tubular cavity, rich in hydrogen-bond donors and acceptors, these tubular polypyridine ensembles rapidly and selectively transport water at a rate of 1.6×10⁹ H₂O⋅S⁻¹⋅channel⁻¹ and protons at a speed as fast as gramicidin A, with a high rejection of ions.     

英国国家科研与创新署学科交叉研究资助机制及启示

Newly established in 2018, the UK Research and Innovation (UKRI) strengthens the strategic coordination of the UK research and innovation system by bringing together seven Research Councils, Research England, and Innovate UK. Through its nine organizations, UKRI funds multidisciplinary and interdisciplinary research in a number of priority areas. It also runs the Strategic Priorities Fund to support multidisciplinary and interdisciplinary research in strategic areas identified by government policies as well as the Global Challenges Research Fund to promote challenge-led interdisciplinary research needed by developing countries. The UKRI makes significant efforts to engage stakeholders in the development, design, and implementation of multidisciplinary and interdisciplinary programs. It has also developed a range of mechanisms to improve the evaluation of multidisciplinary and interdisciplinary projects. Chinese science and innovation funding agencies could draw upon the UKRI experience from four aspects to advance interdisciplinary research in China.     

半导体纳米复合材料的制备及其光电催化CO2还原

本实验通过模拟植物光合作用,设计制备了新颖的光电联合催化池3D-ZnO/Ni BiVO4/FTO,用电化学沉积法制备了泡沫镍负载的ZnO纳米棒光电阴极和BiVO4光电阳极,以0.1 mol·L^−1 KHCO3水溶液作为电解质,1 mmol·L^−1曙红Y为光敏剂,在−0.6 V硅太阳电池的电压下光电催化还原CO2得到了乙醇、乙酸和甲醇,总产率22.5μmol·L^−1·h^−1·cm^−2。实现了将太阳能贮存为化学能并减少了空气中的CO2,加深了学生对绿色化学和植物Calvin循环机理的理解。     

The unusual tribological behavior of diamond-like carbon films under high vacuum

We fabricate F-doped and F-S-codoped diamond-like carbon (DLC) films using plasma-enhanced chemical vapor deposition system. The hardness, Raman spectra, and high-vacuum tribological behaviors indicate that the films are DLC films. The hardness is close related to the tribological properties of DLC films under high vacuum. The high hardness of DLC films would be helpful for obtaining the long lifetime under high vacuum. The lifetimes of F-S-codoped DLC films are about 120 and 140 seconds, which is attributed to the fast graphitization under high vacuum. The lifetime of F-doped DLC films is prolonged to the value of around 300 and 440 seconds, X-ray photoelectron spectroscopy analysis exhibits the existence of the “adsorption” F, and transmission electron microscopy analysis shows that the “adsorption” F could react with Fe to form layered FeF₂ nanocrystal at the initial sliding, which could be helpful for prolonging the lifetime of F-doped DLC films under high vacuum. This investigation opens a new window to overcome the disadvantage of F, S-doped DLC films under high vacuum.     

Effects of intramolecular hydrogen bonds on phosphorescence emission: A theoretical perspective

Importing intramolecular hydrogen bond in phosphorescent transition metal complexes has been considered one of the excellent approaches to improve the electroluminescence performance of organic light-emitting diodes in real applications. However, the relationships between such H-bond structure and phosphorescent properties have not been theoretically revealed yet. In this study, two types of intramolecular hydrogen bonds are introduced into the two classes of traditional materials, that is, Pt(II) and Ir(III) complexes ( 1a and 2a ) to completely elucidate their influence on the structures and properties by comparing with the original phosphors ( 1b and 2b ) using density functional theory/time-dependent density functional theory for the first time. A comprehensive analysis of the geometric structures, molecular orbitals, and luminescence properties (including phosphorescence emission wavelengths and radiative and nonradiative decay processes) has been carried out. Our theoretical model highlights that complexes 1a and 2a embedded with H-bonds significantly promote the phosphorescence emission band blue-shifted and restrict molecular deformations compared with the corresponding 1b and 2b , which can provide helpful guidance to regulate and design several aspects of highly efficient blue phosphorescent emitters.