Pd‐catalyzed desulfitative Hiyama coupling with sulfonyl chlorides

Palladium‐catalyzed desulfitative Hiyama cross‐coupling reactions of various arylsulfonyl chlorides with aryltriethoxysilane have been achieved in good yields. The reported cross‐coupling reactions are tolerant to the common functional groups regardless of electron‐withdrawing or electron‐donating, making these transformations attractive alternatives to the traditional cross‐coupling approaches. Copyright © 2014 John Wiley & Sons, Ltd.     

A novel lipid droplets-targeting fluorescent probe based on dicyanisophorone and carbazole for Cu2+ and its application

A novel fluorescent probe, LCH , based on dicyanisophorone and carbazole, was prepared for the visual detection of Cu²⁺. The probe LCH could recognize Cu²⁺ by fluorescence quenching in EtOH/H₂O (1/4, v/v) solution, which could be easily identified under the 365 nm UV lamp, and the detection limit was as low as 0.785 μM. The recognition mechanism of probe LCH with Cu²⁺ was determined by combining ¹H NMR titration, MS, and theoretical calculations. Practical application experiments showed that probe LCH could be used to detect Cu²⁺ in the test strip experiments. Cell imaging experiments showed that the probe LCH owned good cell permeability and could be applied to the imaging of Cu²⁺ in HepG2 cells. In addition, fluorescence colocalization experiments showed that LCH could target lipid droplets. These results indicate that the probe LCH will have a good application prospect in environmental detection and clinical medicine.     

Three-Dimensional Covalent Organic Frameworks: From Synthesis to Applications

Three-dimensional covalent organic frameworks (3D COFs) with spatially periodic networks demonstrate significant advantages over their 2D counterparts, including enhanced specific surface areas, interconnected channels, and more sufficiently exposed active sites. Nevertheless, research on these materials has met an impasse due to serious problems in crystallization and stability, which must be solved for practical applications. In this Minireview, we first summarize some strategies for preparing functional 3D COFs, including crystallization techniques and functionalization methods. Hereafter, applications of these functional materials are presented, covering adsorption, separation, catalysis, fluorescence, sensing, and batteries. Finally, the future challenges and perspectives for the development of 3D COFs are discussed.     

A simple and rapid route for synthesizing the nanosized g-C3N4 materials with narrow bandgap and their photocatalytic activity

The graphitic carbon nitride (g-C₃N₄) materials with many intriguing properties have attracted much attention in photocatalysis. The photocatalytic activity of g-C₃N₄ is hindered by serious aggregation and limited exposed active sites. Herein is shown that nanosized g-C₃N₄ can be simply obtained by a superfast high-pressure homogenization approach. The high-pressure homogenization treatment can provide strong force to cut and/or to exfoliate the bulk g-C₃N₄ into nanosized g-C₃N₄ with good dispersion. Moreover, choosing different solvents during treatment can cause a different surface structure of as-prepared nanosized g-C₃N₄. In addition, the narrow bandgap properties, the high photogenerated charge carrier separation, and the transport abilities are achieved in as-prepared nanosized g-C₃N₄ because of the retaining conjugated C₃N₄ system. Specifically, the photocatalytic activities of as-prepared nanosized g-C₃N₄ have been significantly enhanced in terms of degradation of organic dye Rhodamine B (RhB) under visible light irradiation (10 times higher than that of bulk g-C₃N₄). These findings can provide a promising and simple approach to the exfoliation, nanonization, and surface functionalization of 2D layered materials.     

Does Perdeuteration Increase the Polarity of Janus Face Cycloalkanes?

Stimulated by a suggestion of the late Professor Jack D. Dunitz, that perdeuterated Janus face cycloalkanes may be more polar than their unlabelled forms, the deuterated isotopologue of all cis-1,2,3,4,5,6-hexafluorocyclohexane ([²H₆]- 1a ) and all cis-1,2,3,4-tetrafluorocyclopentane ([²H₆]- 3a ) were prepared. Computation at the B3LYP−D3 level indicated that [²H₆]- 1a is not more polar than its protio form 1, however perdeuterated cyclopentane [²H₆]- 3a may indeed be more polar than 3 , although the magnitude is predicted to be small. None-the-less retention time analysis on a reverse phase GC/MS column of an add-mix of 3 and [²H₆]- 3a gave some indication that the per-deuterated isotopologue 3a was detected marginally before the unlabelled compound consistent with increased polarity associated with perdeuteration.     

Polyvinyl alcohol-modified graphene oxide as a support for bimetallic Pt–Pd electrocatalysts to enhance the efficiency of formic acid oxidation

The aim of this research was to study the efficiency of polyvinyl alcohol (PVA)-modified graphene oxide (GO) as a supporting material for catalysts that oxidize formic acid. The active metal catalysts (e.g., Pt and Pd) were electrodeposited on PVA/GO surfaces. The morphologies of the prepared catalysts were characterized by scanning electron microscopy and transmission electron microscopy, while their chemical compositions were identified by X-ray diffraction and X-ray photoelectron spectroscopy. The results show that compared with the other catalysts on GO, the prepared active PtPd alloy catalyst nanoparticles with 11.49–20.73 nm sizes were well dispersed on the PVA/GO surfaces. Electrochemical results indicate that the activities of the catalysts with PVA provided a higher current density than that of the catalysts without PVA. The bimetallic 3Pt3Pd/PVA/GO catalyst showed the greatest catalytic activity, stability, and CO oxidation when compared to those of other catalysts. The electronic, morphological, and structural properties promote the mass-charge transfer through the interaction. These results indicate that the PVA-modified GO provides a suitable site for active bimetallic catalyst surfaces, resulting in excellent formic acid oxidation and high CO elimination. The 3Pt3Pd/PVA/GO electrocatalyst is promising for enhancing formic acid oxidation.     

Mapping the Complete Photocycle that Powers a Large Stokes Shift Red Fluorescent Protein

Large Stokes shift (LSS) red fluorescent proteins (RFPs) are highly desirable for bioimaging advances. The RFP mKeima, with coexisting cis- and trans-isomers, holds significance as an archetypal system for LSS emission due to excited-state proton transfer (ESPT), yet the mechanisms remain elusive. We implemented femtosecond stimulated Raman spectroscopy (FSRS) and various time-resolved electronic spectroscopies, aided by quantum calculations, to dissect the cis- and trans-mKeima photocycle from ESPT, isomerization, to ground-state proton transfer in solution. This work manifests the power of FSRS with global analysis to resolve Raman fingerprints of intermediate states. Importantly, the deprotonated trans-isomer governs LSS emission at 620 nm, while the deprotonated cis-isomer's 520 nm emission is weak due to an ultrafast cis-to-trans isomerization. Complementary spectroscopic techniques as a table-top toolset are thus essential to study photochemistry in physiological environments.     

Enhanced Four-Electron Oxygen Reduction Selectivity of Clamp-Shaped Cobalt(II) Porphyrin(2.1.2.1) Complexes

The molecular structure, electrochemistry, spectroelectrochemistry and electrocatalytic oxygen reduction reaction (ORR) features of two Co^II porphyrin(2.1.2.1) complexes bearing Ph or F₅Ph groups at the two meso-positions of the macrocycle are examined. Single crystal X-ray analysis reveal a highly bent, nonplanar macrocyclic conformation of the complex resulting in clamp-shaped molecular structures. Cyclic voltammetry paired with UV/Vis spectroelectrochemistry in PhCN/0.1 M TBAP suggest that the first electron addition corresponds to a macrocyclic-centered reduction while spectral changes observed during the first oxidation are consistent with a metal-centered Co^II/Co^III process. The activity of the clamp-shaped complexes towards heterogeneous ORR in 0.1 M KOH show selectivity towards the 4e⁻ ORR pathway giving H₂O. DFT first-principle calculations on the porphyrin catalyst indicates a lower overpotential for 4e⁻ ORR as compared to the 2e⁻ pathway, consistent with experimental data.     

Pulsed Electrocatalysis Enabling High Overall Nitrogen Fixation Performance for Atomically Dispersed Fe on TiO2

Atomically dispersed Fe was designed on TiO₂ and explored as a Janus electrocatalyst for both nitrogen oxidation reaction (NOR) and nitrogen reduction reaction (NRR) in a two-electrode system. Pulsed electrochemical catalysis (PE) was firstly involved to inhibit the competitive hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Excitingly, an unanticipated yield of 7055.81 μmol h⁻¹ g⁻¹_cat. and 12 868.33 μmol h⁻¹ g⁻¹_cat. were obtained for NOR and NRR at 3.5 V, respectively, 44.94 times and 7.8 times increase in FE than the conventional constant voltage electrocatalytic method. Experiments and density functional theory (DFT) calculations revealed that the single-atom Fe could stabilize the oxygen vacancy, lower the energy barrier for the vital rupture of N≡N, and result in enhanced N₂ fixation performance. More importantly, PE could effectively enhance the N₂ supply by reducing competitive O₂ and H₂ agglomeration, inhibit the electrocatalytic by-product formation for longstanding *OOH and *H intermediates, and promote the non-electrocatalytic process of N₂ activation.     

Atomization-Induced High Intrinsic Activity of a Biocompatible MgAl-LDH Supported Ru Single-Atom Nanozyme for Efficient Radicals Scavenging

Developing efficient nanozymes to mimic natural enzymes for scavenging reactive radicals remains a significant challenge owing to the insufficient activity of conventional nanozymes. Herein, we report a novel Ru single-atom nanozyme (SAE), featuring atomically dispersed Ru atoms on a biocompatible MgAl-layered double hydroxide (Ru₁/LDH). The prepared Ru₁/LDH SAE shows high intrinsic peroxidase (POD)-like catalytic activity, which outperforms the Ru nanoclusters (NCs) nanozyme by a factor of 20 and surpasses most SAEs. The density functional theory calculations reveal that the high intrinsic POD-like activity of Ru₁/LDH can be attributed to a heterolytic path of H₂O₂ dissociation on the single Ru sites, which requires lower free energy (0.43 eV) compared to the homolytic path dissociation on Ru NC (0.63 eV). In addition, the Ru₁/LDH SAE shows excellent multiple free radicals scavenging ability, including superoxide anion radical (O₂⋅⁻), hydroxyl radical (⋅OH), nitric oxide radical (NO⋅) and 2, 2-diphenyl-1-picrylhydrazyl radical (DPPH⋅). Given the advantages of Ru₁/LDH with high enzymatic activities, biosafety, and ease to scale up, it paves the way for exploring SAEs in the practical biological immunity system.