D-π-A array structure of Bi4Ti3O12-triazine-aldehyde group benzene skeleton for enhanced photocatalytic uranium (VI) reduction.

Photocatalytic reduction of UVI to UIV can help remove U from the environment and thus reduce the harmful impacts of radiation emitted by uranium isotopes. Herein, we first synthesized Bi4Ti3O12 (B1) particles, then B1 was crosslinked with 6-chloro-1,3,5-triazine-diamine (DCT) to afford B2. Finally, B3 was formed using B2 and 4-formylbenzaldehyde (BA-CHO) to investigate the utility of the D-π-A array structure for photocatalytic UVI removal from rare earth tailings wastewater. B1 lacked adsorption sites and displayed a wide band gap. The grafted triazine moiety in B2 introduced active sites and narrowed the band gap. Notably, B3, a Bi4Ti3O12 (donor)-triazine unit (π-electron bridge)-aldehyde benzene (acceptor) molecule, effectively formed the D-π-A array structure, which formed multiple polarization fields and further narrowed the band gap. Therefore, UVI was more likely to capture electrons at the adsorption site of B3 and be reduced to UIV due to energy level matching effects. UVI removal capacity of B3 under simulated sunlight was 684.9 mg g-1, 2.5 times greater than B1 and 1.8 times greater than B2. B3 was still active after multiple reaction cycles, and UVI removal from tailings wastewater reached 90.8%. Overall, B3 provides an alternative design scheme for enhancing photocatalytic performance.

Biomimetic Photocatalytic System Designed by Spatially Separated Cocatalysts on Z-scheme Heterojunction with Identified Charge-transfer Processes for Boosting Removal of U(VI).

Designing highly efficient photocatalysts with rapid migration of photogenerated charges and surface reaction kinetics for the photocatalytic removal of uranium (U(VI)) from uranium mine wastewater remains a significant challenge. Inspired by natural photosynthesis, a biomimetic photocatalytic system is assembled by designing a novel hollow nanosphere MnOx @TiO2 @CdS@Au (MTCA) with loading MnOx and Au nano particles (Au NPs) cocatalysts on the inner and outer surfaces of the TiO2 @CdS. The spatially separated cocatalysts efficiently drive the photogenerated charges to migrate in opposite directions, while the Z-scheme heterogeneous shell further separates the interfacial charges. Theoretical calculation identifies multiple consecutive forward charge transfers without charge recombination within MTCA. Thus, MTCA could efficiently remove 99.61% of U(VI) after 15 min of simulated sunlight irradiation within 3 mmol L-1 NaHCO3 with 0.231 min-1 of the reduction rate constant, outperforming most previously reported photocatalysts. MTCA further significantly removes 91.83% of U(VI) from the natural uranium mining wastewater under sunlight irradiation. This study provides a novel approach to designing an ideal biomimetic photocatalyst for remediating environmental pollution.

Realizing All-Climate Li-S Batteries by Using a Porous Sub-Nano Aromatic Framework.

Lithium-sulfur (Li-S) batteries with high energy density are currently receiving enormous attention. However, their redox kinetics at low temperature is extremely tardy, and polysulfides shuttling is serious at high temperature, which severely hinders the implementation of wide-temperature Li-S batteries. Herein, we propose an all-climate Li-S battery based on an ether-based electrolyte by using a porous sub-nano aromatic framework (SAF) modified separator. It's demonstrated that the fully conjugated SAF-3 with a small pore size (0.97 nm) and narrow band gap (1.72 eV) could efficiently block the polysulfides shuttling at elevated temperature and boost the polysulfides conversion at low temperature. Consequently, the SAF-3 modified cells work well in a wide temperature ranging from -40 to 60 °C. Furthermore, when operated at room temperature, the modified cell exhibits 90 % capacity retention over 100 cycles under high-sulfur loading (5.0 mg cm-2 ) and lean electrolyte (5 µL mg-1 ).

Two quinoline-based two-photon fluorescent probes for imaging of viscosity in subcellular organelles of living HeLa cells.

Two viscosity-sensitive two-photon fluorescent probes (QL and QLS) were designed and synthesized, which can be localized in lysosome and mitochondria in living HeLa cells, respectively. As the increases of viscosity from 2.55 to 1150 cP, the fluorescence quantum yield (Φ) of QL and QLS was increased by 28-fold and 37-fold, respectively. At the same time, its effective two-photon absorption cross section (ΦδTPA) was enhanced by 15-fold and 16-fold, respectively. Fluorescence lifetime imaging (FLIM) of living HeLa cells stained with QL and QLS, revealed that lysosomal viscosity ranged from 100.76 to 254.74 cP and mitochondrial viscosity ranged from 92.21 to 286.79 cP. This type of fluorescent probe is helpful in the design and application of materials for monitoring diseases associated with abnormal viscosity.

Construction of polymeric carbon nitride and dibenzothiophene dioxide-based intramolecular donor-acceptor conjugated copolymers for photocatalytic H2 evolution.

Polymeric carbon nitride (g-C3N4) has succeeded as a striking visible-light photocatalyst for solar-to-hydrogen energy conversion, owing to its economical attribute and high stability. However, due to the lack of sufficient solar-light absorption and rapid photo-generated carrier recombination, the photocatalytic activity of raw g-C3N4 is still unsatisfactory. Herein, new intramolecular g-C3N4-based donor-acceptor (D-A) conjugated copolymers have been readily synthesized by a nucleophilic substitution/condensation reaction between urea and 3,7-dihydroxydibenzo[b,d]thiophene 5,5-dioxide (SO), which is strategically used to improve the photocatalytic hydrogen evolution performance. The experimental results demonstrate that CNSO-X not only improves light utilization, but also accelerates the spatial separation efficiency of the photogenerated electron-hole pairs and increases the wettability with the introduction of SO. In addition, the adsorption energy barrier of CNSO-X to H* has a significant reduction via theoretical calculation. As expected, the CNSO-20 realizes the best photocatalytic H2 evolution activity of 251 µmol h-1 (50 mg photocatalyst, almost 8.5 times higher than that of pure CN) with an apparent quantum yield of 10.16% at 420 nm, which surpasses most strategies for the organic molecular copolymerization of carbon nitride. Therefore, this strategy opens up a novel avenue to develop highly efficient g-C3N4 based photocatalysts for hydrogen production.

A self-assembled perylene diimide nanobelt for efficient visible-light-driven photocatalytic H2 evolution.

In this communication, a self-assembled supramolecular system consisting of phosphoric acid substituted perylene diimide (P-PMPDI) has been successfully developed for highly efficient photocatalytic hydrogen evolution. Compared with a carboxylic substituent perylene diimide (P-CMPDI), P-PMPDI showed a superior H2 evolution reaction rate of 11.7 mmol g-1 h-1 and a recorded apparent quantum yield (AQY) of 2.96% at 550 nm.

Enhanced Photocurrent via π-Bridge Extension of Perylenemonoimide-Based Dyes for p-Type Dye-Sensitized Solar Cells and Photoelectrochemical Cells.

Two dyes TB and TSB containing triphenylamine as the donor and perylenemonoimide as the acceptor, with and without bithiophene as π-bridge, respectively, were successfully prepared and characterized for p-type dye-sensitized solar cells (p-DSSCs) and dye-sensitized photoelectrochemical cells (DS-PECs). As a result, TSB with bithiophene π-bridge exhibited a broader absorption spectrum and a higher molar extinction coefficient than TB. Furthermore, the photocurrents of p-DSSCs and DS-PECs for the dye TSB were increased by 26.9 and 32.9%, respectively, compared with those of the dye TB. Meanwhile, the electrochemical impedance spectroscopy of the TSB-based p-DSSC showed the smaller charge-transfer resistance and larger hole lifetime because the longer π-bridge facilitated charge transfer and separation within the dye molecule and effectively prevented the hole recombination process at the NiO/dye interface, resulting in improvement of photoelectric performance. Hence, these results show that the π-bridge extension of dyes has a promising effect on the photocurrent improvement of p-DSSCs and DS-PECs.

Targetable N-annulated perylene-based colorimetric and ratiometric near-infrared fluorescent probes for the selective detection of hydrogen sulfide in mitochondria, lysosomes, and serum.

Hydrogen sulfide (H2S) serves an effective role in biological systems as the acknowledged third endogenous gasotransmitter, so it makes great sense to detect and analyze H2S sensitively and quantitatively in subcellular environments, such as in mitochondria and lysosomes where H2S is widespread and functions as the mediator. Considering the excellent photophysical properties and multiple modification sites, N-annulated perylene (NP) was firstly chosen as the fluorophore to design a series of colorimetric and ratiometric near-infrared (NIR) fluorescent probes for the sensitive and selective detection of H2S. The probes showed near-infrared fluorescence at 681 nm in the absence of H2S. But with the addition of H2S, the NIR fluorescence decreased sharply and a new fluorescence peak at approximately 481 nm dramatically increased in a short response time, which could be clearly observed using the naked eye. Their large ratiometric fluorescence changes (about 200 nm), excellent selectivity and stability would be helpful for its detection in biological systems, and the limit of detection of the probe was calculated down to 139 nM. The reaction mechanism was studied as well. The targetable probes (Mito-NPNM and Lyso-NPNM) were also successfully employed to detect endogenous H2S in the mitochondria and lysosomes of living cells respectively. Besides, these probes were successfully applied to quantify H2S at low concentrations in serum where H2S levels are of great significance as an important indicator of various diseases.

Enhanced Photocurrent Density by Spin-Coated NiO Photocathodes for N-Annulated Perylene-Based p-Type Dye-Sensitized Solar Cells.

The low photocurrent density of p-type dye-sensitized solar cells (p-DSSCs) has limited the development of high-efficiency tandem cells due to the inadequate light-harvesting ability of sensitizers and the low hole mobility of semiconductors. Hereby, two new "push-pull" type organic dyes (PQ-1 and PQ-2) containing N-annulated perylene as electron donor have been synthesized, where the PQ-2-based p-DSSCs show higher photoelectric conversion efficiency (PCE) of 0.316% owing to the higher molar extinction compared to of that PQ-1. Additionally, the photocurrent densities were remarkably increased from 2.20 to 5.85 mA cm(-2) for PQ-1 and 2.45 to 6.69 mA cm(-2) for PQ-2 by spin-coated NiO photocathode based-p-DSSCs, respectively. This results are ascribed to the enhancement of hole transport rate, dye-loading amounts and transparency of NiO films in comparison to that prepared by screen-printing method. Electrochemical impedance spectroscopy and theoretical calculations studies indicate that the molecular dipole moment approaching closer to the NiO surface shifts the quasi-Fermi level to more positive levels, improving open-circuit voltage (Voc). Intensity-modulated photocurrent spectroscopy illustrates that the hole transit time in NiO films prepared in spin-coating is shorter than that prepared by screen-printing method.

[Changes of serum IL-1, IL-2R and TNF-alpha levels in divers after 150 m Heliox saturation -182 m excursion in the open sea diving].

OBJECTIVE: To observe the change of the serum IL-1, IL-2R and TNF-alpha levels in divers after deep saturation in the open sea diving. METHOD: Eight divers experienced 150 in Heliox saturation -182 in excursion diving. Serum levels of IL-1, IL-2R and TNF-alpha level before and after diving were measured by ELISA. RESULTS: There was no significant change of serum TNF-alpha level after saturation diving, but serum levels of IL-1, IL-2R increased significantly after saturation diving. CONCLUSION: Deep open sea saturation diving had significant effects on serum IL-6, IL-2R levels of the divers.