Synthesis of palladium complexes derived from imidazolidin‐2‐ylidene ligands and used for catalytic amination reactions

N‐Aryl amination and the Buchwald–Hartwig reaction are of great synthetic and industrial interest and scientists accept their usefulness and versatility for obtaining arylamines. In this study Ag–N‐heterocyclic carbene complexes were used as transmetallation reagents for the synthesis of Pd–N‐heterocyclic carbene complexes. The new Pd–N‐heterocyclic carbene complexes were characterized using elemental analysis and ¹H NMR, ¹³C NMR and infrared spectroscopies. The crystal structure of one, namely dichlorobis[1,3‐bis(2‐methylbenzyl)imidazolidin‐2‐yliden]palladium(II), is presented. The activity of the Pd(II) complexes in the coupling reaction of anilines or amines with bromobenzene was investigated. These complexes exhibited high catalytic activities in the direct synthesis of triarylamines and secondary amines in a single step. Copyright © 2016 John Wiley & Sons, Ltd.     

Preparation of antimicrobial polycaprolactone‐silica composite films with nanosilver rods and triclosan using roll‐milling method

In this study, antimicrobial polycaprolactone composite films containing 12.5% silica and 0.15% silver nanorods were prepared using the roll‐milling method. The destruction of E. coli and S. aureus on the surface of the composite films was evaluated after 6 hr of incubation at 37°C. For the E. Coli, no bacterial contamination was detected after 6 hr and the film surface was completely disinfected with 100% reduction of the microbial contamination. For the S. aureus, 94% reduction of the bacterial contamination was observed after 6 hr. The results were compared with the composite films containing triclosan, a broad‐spectrum antimicrobial agent. The antimicrobial activity tests with 0.25% triclosan incorporated polycaprolactone‐silica composite films showed only 70% reduction of E. coli and 95% reduction of S. aureus after 6 hr. The results demonstrated that the use of silver nanoparticles in the biopolymer industry has huge potential for the self‐cleaning applications. Copyright © 2009 John Wiley & Sons, Ltd.     

Adsorption properties and synthesis of silica aerogel-hollow silica microsphere hybrid (sandwich) structure

Journal of Sol-Gel Science and Technology - Silica aerogels have the potential use in many applications due to their large specific surface area and high porosity. One of these applications can be...     

Front Cover: Twisting versus Delocalization in CAAC- and NHC-Stabilized Boron-Based Biradicals: The Roles of Sterics and Electronics (Chem. Eur. J. 16/2021)

Invited for the cover of this issue is Bernd Engels, Holger Braunschweig, Volker Engel and their coworkers at University of Würzburg. The image depicts bridged boron compounds which possess fascinating relationships between their composition and their geometrical and electronic structures, the latter ranging from closed-shell to biradical triplet or singlet ground state. Read the full text of the article at 10.1002/chem.202004619 .     

Halogen-Bonded BODIPY Frameworks with Tunable Optical Features**

The ability to tune the optical features of BODIPY materials in the solid state is essential for their photorelated application and requires efficient control of the crystal packing. In this study, such control of BODIPY supramolecular assemblies was achieved by deliberate design and synthesis of a BODIPY containing a strong halogen-bond (XB) acceptor (−NO₂) and donor (I, Br) to mediate XB interactions. The di-halogenated structures formed isostructural mono-coordinate motif B3 , B4 (1D tubular structure) and symmetric bifurcated motif B4-II (1D zigzag chains structure) through N−O⋅⋅⋅I, Br XB interactions. These XB interactions promote singlet-to-triplet intersystem crossing and triplet-to-singlet reverse intersystem crossing due to partial delocalization of oxygen electrons onto Br and I, which leads to unexpected fluorescence enhancement of B4-II . Finally, the indirect optical band gaps of B3 , B4 and B4-II were amenable to tuning in the range of 1.85–2.50 eV by XB-driven crystal packings.     

Distinctive MS/MS Fragmentation Pathways of Glycopeptide‐Generated Oxonium Ions Provide Evidence of the Glycan Structure

Post‐translational glycosylation of proteins play key roles in cellular processes and the site‐specific characterisation of glycan structures is critical to understanding these events. Given the challenges regarding identification of glycan isomers, glycoproteomic studies generally rely on the assumption of conserved biosynthetic pathways. However, in a recent study, we found characteristically different HexNAc oxonium ion fragmentation patterns that depend on glycan structure. Such patterns could be used to distinguish between glycopeptide structural isomers. To acquire a mechanistic insight, deuterium‐labelled glycopeptides were prepared and analysed. We found that the HexNAc‐derived m/z 126 and 144 oxonium ions, differing in mass by H₂O, had completely different structures and that high‐mannose N‐glycopeptides generated abundant Hex‐derived oxonium ions. We describe the oxonium ion decomposition mechanisms and the relative abundance of oxonium ions as a function of collision energy for a number of well‐defined glycan structures, which provide important information for future glycoproteomic studies.