o-Trityl phenoxy-imino vanadium (III) complexes: synthesis,characterization, and catalysis on ethylene (co)polymerization

Several phenoxy-imine ligands bearing o-trityl group in phenoxy moiety RN=CHArOH (Ar = C₆H₂(CPh₃)^tBu, R = 2,6-Me₂C₆H₃ ( L ₁ H ); 2,6-ⁱPr₂C₆H₃ ( L ₂ H ); 3,5-(CF₃)₂C₆H₃ ( L ₃ H ); 3,5-(OMe)₂C₆H₃ ( L ₄ H ); CHPh₂ ( L ₅ H ); CPh₃ ( L ₆ H )) were synthesized and characterized by¹H NMR and ¹³C NMR spectroscopy. The vanadium complexes based on these ligands LVCl₂(THF)₂ ( 1–6 ) were synthesized via conventional transmetalation reaction in moderate to high yields. Complexes 1–6 were fully characterized by FT-IR, elemental analyses and the molecular structures of 1 , 2 ·H₂O, (2 ·H₂O ) ₂ (μ-Cl) ₂ , 4 , and 5 were confirmed by X-ray crystallographic analysis in which the six-coordinated vanadium centers are in a typical octahedral geometry. Upon activation with Et₂AlCl in toluene, complexes 1–6 showed high activities in ethylene polymerization affording polymers with moderate molecular weight (5.9–11.8 × 10⁴ Da). Moreover, in hexane or CH₂Cl₂, 1–6 /Et₂AlCl exhibited enhanced activities. When activated with MAO or MMAO in toluene, these complexes showed relatively low activities but afforded polymers with ultra-high molecular weight (up to 3.30 × 10⁶ Da). 1–6 /Et₂AlCl also showed high activities in ethylene/1-hexene copolymerization at room temperature giving moderate molecular-weight polymers (6.5–11.4 × 10⁴ Da) with co-monomer incorporation being of 6.0 ~ 7.8%.     

An improved LC–MS/MS method for determination of docetaxel and its application to population pharmacokinetic study in Chinese cancer patients

Because of its unpredictable side effects and efficacy, the anticancer drug docetaxel (DTX) requires improved characterisation of its pharmacokinetic profiles through population pharmacokinetic studies. A sensitive and rugged LC–MS/MS method for the detection of DTX in human plasma was developed and optimised using paclitaxel as an internal standard (IS). The plasma samples underwent rapid extraction using hybrid solid-phase extraction-protein precipitation. The analyte and IS were separated with an isocratic system on a Zorbax Eclipse Plus C₁₈ column using water containing 0.05% acetic acid along with 20 μM of sodium acetate and methanol (30/70, v/v) as the mobile phase. Quantification was performed using a triple quadrupole mass spectrometer through multiple reaction monitoring in positive mode, using the m/z 830.3 → 548.8 and m/z 876.3 → 307.7 transitions for DTX and paclitaxel, respectively. The range of the calibration curve was 1–500 ng/mL for DTX, and the linear correlation coefficient was >0.99. The accuracies ranged from −4.6 to 4.2%, and the precision was no higher than 7.0% for the analytes. No significant matrix effect was observed. Both DTX and the IS showed considerable recovery. This method was finally applied to the establishment of a population pharmacokinetic model to optimise the clinical use of DTX.     

Development of Lysosome-Targeted Fluorescent Probes for Cys by Regulating the Boron-dipyrromethene (BODIPY) Molecular Structure

Our previous discovery suggested that substituents on the 1,7 positions delicately modulate the sensing ability of the meso-arylmercapto boron-dipyrromethene (BODIPY) to biothiols. In this work, the impact of delicate modulations on the sensing ability is investigated. Therefore, 1,7-dimethyl, 3,5-diaryl substituted BODIPY is designed and developed and its conformationally restricted species with a meso-arylmercapto moiety ( DM-BDP-SAr and DM-BDP-R-SAr ) as selective fluorescent probes for Cys. Moreover, the lysosome-target probes ( Lyso-S and Lyso-D ) based on DM-BDP-SAr carrying one or two morpholinoethoxy moieties were developed. They were able to detect Cys selectively in vitro with low detection limits. Both Lyso-S and Lyso-D localized nicely in lysosomes in living HeLa cells and exhibited red fluorescence for Cys. Moreover, a novel fluorescence quenching mechanism was proposed from the calculations by density functional theory (DFT). The probes may go through intersystem crossing (from singlet excited state to triplet excited state) to result in fluorescence quenching.     

Facile preparation of Ag/Ag2WO4/g‐C3N4 ternary plasmonic photocatalyst and its visible‐light photocatalytic activity

Introducing plasmonic metals into semiconductor materials has been proven to be an attractive strategy for enhancing photocatalytic activity in the visible region. In this work, a novel and efficient Ag/Ag₂WO₄/g‐C₃N₄ (AACN) ternary plasmonic photocatalyst was successfully synthesized using a facile one‐step in situ hydrothermal method. The composition, structure, morphology and optical absorption properties of AACN were investigated using X‐ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, and UV–visible diffuse reflectance spectroscopy, respectively. Photocatalytic performance of AACN was evaluated via rhodamine B and tetracycline degradation. The results indicated that AACN had excellent photocatalytic performance for rhodamine B degradation with a rate constant of 0.0125 min^?1, which was higher than those of Ag₂WO₄ and Ag/Ag₂WO₄. Characterization and photocatalytic tests showed that the strong coupling effect between the Ag/Ag₂WO₄ nanoparticles and the exfoliated ultrathin g‐C₃N₄ nanosheets was superior for visible‐light responsivity and reduced the recombination rate of photogenerated electrons and holes. A proposed mechanism is also discussed according to the band energy structure and the experimental results.     

Multiple positive solutions for Schrödinger‐Poisson system involving singularity and critical exponent

In this paper, the existence and multiplicity of positive solutions is established for Schrödinger‐Poisson system of the form where 0 ∈ Ω is a smooth bounded domain in , , and λ > 0 is a real parameter. Combining with the variational method and Nehari manifold method, two positive solutions of the system are obtained.     

One-step synthesis of magnetic composite UiO-66/Fe3O4/GO for the removal of radioactive cesium ions

Journal of Radioanalytical and Nuclear Chemistry - In this study, the UiO-66/Fe3O4/GO composite was prepared by one step method for removal of cesium ions (Cs+) in water and exhibited excellent...     

Large‐Area Aminated‐Graphdiyne Thin Films for Direct Methanol Fuel Cells

A two‐dimensional (2D) carbon nanofilm with uniform artificial nanopores is an ideal material to ultimately suppress the fuel permeation in the proton exchange membrane fuel cells. Graphdiyne has great mechanical strength, high dimensional stability, and controllable nanopores, and has good prospects to play this crucial role. It is found that graphdiyne nanofilm with amino groups and natural nanopores can be easily prepared with high integrity. The aminated graphdiyne has good compatibility with the Nafion matrix owing to the acid–base interaction between them. The excellent comprehensive properties of graphdiyne in selectivity, dimensional stability, and integrity effectively improve the power performance and stability of fuel cells at wide temperature. Our results can be developed into a universal method that can easily realize the selective separation of ions and small molecules, and open a new way for the emerging applications in green energy.     

Elucidating Molecule–Plasmon Interactions in Nanocavities with 2 nm Spatial Resolution and at the Single‐Molecule Level

The fundamental understanding of the subtle interactions between molecules and plasmons is of great significance for the development of plasmon‐enhanced spectroscopy (PES) techniques with ultrahigh sensitivity. However, this information has been elusive due to the complex mechanisms and difficulty in reliably constructing and precisely controlling interactions in well‐defined plasmonic systems. Herein, the interactions in plasmonic nanocavities of film‐coupled metallic nanocubes (NCs) are investigated. Through engineering the spacer layer, molecule–plasmon interactions were precisely controlled and resolved within 2 nm. Efficient energy exchange interactions between the NCs and the surface within the 1–2 nm range are demonstrated. Additionally, optical dressed molecular excited states with a huge Lamb shift of ≈7 meV at the single‐molecule (SM) level were observed. This work provides a basis for understanding the underlying molecule–plasmon interaction, paving the way for fully manipulating light–matter interactions at the nanoscale.     

Unveiling the Layer‐Dependent Catalytic Activity of PtSe2 Atomic Crystals for the Hydrogen Evolution Reaction

Two‐dimensional (2D) PtSe₂ shows the most prominent layer‐dependent electrical properties among various 2D materials and high catalytic activity for hydrogen evolution reaction (HER), and therefore, it is an ideal material for exploring the structure–activity correlations in 2D systems. Here, starting with the synthesis of single‐crystalline 2D PtSe₂ with a controlled number of layers and probing the HER catalytic activity of individual flakes in micro electrochemical cells, we investigated the layer‐dependent HER catalytic activity of 2D PtSe₂ from both theoretical and experimental perspectives. We clearly demonstrated how the number of layers affects the number of active sites, the electronic structures, and electrical properties of 2D PtSe₂ flakes and thus alters their catalytic performance for HER. Our results also highlight the importance of efficient electron transfer in achieving optimum activity for ultrathin electrocatalysts. Our studies greatly enrich our understanding of the structure–activity correlations for 2D catalysts and provide new insight for the design and synthesis of ultrathin catalysts with high activity.