Olefin Cycloadditions of the Electrophilic Phosphinidene Complex [iPr2N−P=Fe(CO)4]

Highly strained methylenephosphiranes are formed in the reaction of the new electrophilic phosphinidene complex [iPr₂N−P=Fe(CO)₄] with allenes. Remarkably, reaction with diallenes at 0°C also leads to a phosphirane, which rearranges upon warming to room temperature to a bis-isopropylidenephospholene (see scheme).     

Polynaphthylimide–Azomethines Containing Triphenylamine or Carbazole Moieties with Tuned Optoelectronic Properties through Molecular Design

Polyazomethines containing electron-donor triphenylamine (TPA) or carbazole (Cbz) and electron-acceptor naphthyl(di)imide were synthesized and investigated with regard to thermal, optical and electronic features, with a focus on their modulation by molecular design. The polycondesation of an imido-based diamine with a Cbz- or TPA-based dialdehyde led to donor-acceptor polymers with good thermostability, up to 318 °C. These displayed good solubility in organic solvents, which enabled easy polymer processability in thin films with different molecular assemblies. The molecular order improved the charge carrier’s mobility, with a direct impact on the bandgap energy. The optical properties studied by UV–Vis absorption and fluorescence experiments showed solvent-dependence, characteristic for donor-acceptor systems. The structural parameters exerted a strong influence on the light-emissive behavior, with the prevalence of intrinsic or intramolecular charge transfer fluorescence contingent on the donor-acceptor strength and polymer geometry. All polymers showed good electroactivity, supporting both electrons and holes transport. The exchange of Cbz with TPA proved to be an efficient tool with which to decrease the bandgap energy, while that of naphthyl(di)imide with bis(naphthylimide) was beneficial for fluorescence enhancement. This study may contribute to a deeper understanding of the physico-chemistry of electronic materials so as to make them more competitive in the newest energy-related or other optoelectronic devices.     

Ditopic Chelators of Dicopper Centers for Enhanced Tyrosinases Inhibition

Tyrosinase enzymes (Tys) are involved in the key steps of melanin (protective pigments) biosynthesis and molecules targeting the binuclear copper active site on tyrosinases represent a relevant strategy to regulate enzyme activities. In this work, the possible synergic effect generated by a combination of known inhibitors is studied. For this, derivatives containing kojic acid (KA) and 2-hydroxypyridine-N-oxide (HOPNO) combined with a thiosemicarbazone (TSC) moiety were synthetized. Their inhibition activities were evaluated on purified tyrosinases from different sources (mushroom, bacterial, and human) as well as on melanin production by lysates from the human melanoma MNT-1 cell line. Results showed significant enhancement of the inhibitory effects compared with the parent compounds, in particular for HOPNO-TSC. To elucidate the interaction mode with the dicopper(II) active site, binding studies with a tyrosinase bio-inspired model of the dicopper(II) center were investigated. The structure of the isolated adduct between one ditopic inhibitor (KA-TSC) and the model complex reveals that the binding to a dicopper center can occur with both chelating sites. Computational studies on model complexes and docking studies on enzymes led to the identification of KA and HOPNO moieties as interacting groups with the dicopper active site.     

Application of proton field-cycling NMR relaxometry for studying translational diffusion in simple liquids and polymer melts

With the availability of commercial field-cycling relaxometers together with progress of home-built instruments nuclear magnetic resonance relaxometry has gained new momentum as a method of investigating the dynamics in viscous liquids and polymer melts. The method provides the frequency dependence of the spin–lattice relaxation rate. In the case of protons, one distinguishes intramolecular and intermolecular relaxation pathways. Whereas the intramolecular contribution prevails at high frequencies and reflects rotational dynamics, the often ignored intermolecular relaxation contribution dominates at low-frequency and provides access to translational dynamics. A universal low-frequencies dispersion law holds which in pure systems allows determining the diffusion coefficient in a straightforward way. In addition, the rotational time constant is extracted from the high-frequency relaxation contribution. This is demonstrated for simple and ionic liquids and for polymer melts.     

Analysis of a Simplified Model of Rigid Structure Floating in a Viscous Fluid

Journal of Nonlinear Science - We study the interaction of surface water waves with a floating solid constraint to move only in the vertical direction. The first novelty we bring in is that we...