Synthesis and characterization of a biphenyl-linked hemicryptophane and an endohedral cobalt(II) complex

Hemicryptophanes are covalent molecular cages, constructed from a cyclotriveratrylene-based host unit and a functional unit linked by covalent spacers, which have been designed to accommodate endohedral functionalities in the cavity. In this study, the synthesis and characterization of the rigid, biphenyl-linked hemicryptophane 1 were investigated by NMR, ESI-MS, and X-ray crystallography. The structure of the inclusion complex, in which a dichloromethane molecule was constructed encapsulated within 1, was characterized by X-ray crystallography. An endohedral, cobalt(II) hemicryptophane complex 2 was also synthesized and characterized ESI-MS and X-ray crystallography. The X-ray crystal structure of 2 showed that the biphenyl-linked hemicryptophane had three components—a molecule each of chloroform and acetonitrile, and a cobalt(II) ion—within its cavity.     

Exploiting the Potential of Meroterpenoid Cyclases to Expand the Chemical Space of Fungal Meroterpenoids

Fungal meroterpenoids are a diverse group of hybrid natural products with impressive structural complexity and high potential as drug candidates. In this work, we evaluate the promiscuity of the early structure diversity-generating step in fungal meroterpenoid biosynthetic pathways: the multibond-forming polyene cyclizations catalyzed by the yet poorly understood family of fungal meroterpenoid cyclases. In total, 12 unnatural meroterpenoids were accessed chemoenzymatically using synthetic substrates. Their complex structures were determined by 2D NMR studies as well as crystalline-sponge-based X-ray diffraction analyses. The results obtained revealed a high degree of enzyme promiscuity and experimental results which together with quantum chemical calculations provided a deeper insight into the catalytic activity of this new family of non-canonical, terpene cyclases. The knowledge obtained paves the way to design and engineer artificial pathways towards second generation meroterpenoids with valuable bioactivities based on combinatorial biosynthetic strategies.     

The N-soliton solution of a two-component modified nonlinear Schrödinger equation

The N-soliton solution is presented for a two-component modified nonlinear Schrödinger equation which describes the propagation of short pulses in birefringent optical fibers. The solution is found to be expressed in terms of determinants. The proof of the solution is carried out by means of an elementary theory of determinants. The generalization of the 2-component system to the multi-component system is discussed as well as a (2+1)-dimensional nonlocal equation arising from its continuum limit.     

Preparation of thermoplastic elastomer from natural rubber grafted with polystyrene

Thermoplastic elastomer was prepared from deproteinized natural rubber (DPNR) by graft-copolymerization of styrene, which was performed onto rubber particles of about 1 μm in diameter in latex stage with tert-butyl hydroperoxide/tetraethylenepentamine as an initiator. Suitable initiator concentrations were determined to be 3.3 × 10⁻² and 20 × 10⁻² mol/kg-rubber for the graft-coplymerization of styrene of 1.5 and 5.5 mol/kg-rubber, respectively, in which conversion and grafting efficiency of styrene were more than 90 mol% and 80 mol%, respectively. The resulting polystyrene, grafted onto the rubber particles, was characterized by size exclusion chromatography after ozonolysis. Morphology of the DPNR grafted with polystyrene (DPNR-graft-PS) was observed by transmission electron microscopy (TEM). Change in morphology after processing the DPNR-graft-PS at 150 °C was associated with change in mechanical properties, i.e. stress at strain of 1 and stress at break. The outstanding mechanical properties, maintained even after processing, were assigned to the thermoplasticity of the DPNR-graft-PS, based on the high conversion and high grafting efficiency.