The thioacetate approach to the synthesis of the side chain of vitamin D metabolites and analogues

We describe an efficient synthesis of thia analogues of the vitamin D side chain that is based on the in situ generation of a thiolate anion and its alkylation with electrophiles.     

One‐Step Synthetic Access to Isosteric and Potent Anticancer Nitrogen Heterocycles with the Benzo[c]phenanthridine Scaffold

A versatile one‐step two‐component cyclization to build new tetracyclic nitrogen heterocycles is described. Ortho‐methylhetarenecarbonitrile components were condensed with aldehydes to access a large library of differently substituted ring systems. The heterocyclic core can be easily modified by variation of the position of the endocyclic nitrogen atom in the o‐methylhetarenecarbonitrile substrate. The manner of the nucleophilic attack that leads to the condensation can be triggered by different electron‐density distribution in the molecule induced by the position of the nitrogen atom. Taking this into account, there is an electronic preference that leads to either pyridophenanthrolines or the corresponding pyridoazacarbazoles as the main products. We demonstrate the high antitumor potential of some of our synthesized heterocycles, which is strongly dependent on the substitution pattern introduced through the aldehyde component. The position and number of endocyclic nitrogen atoms play an important role regarding cytotoxicity of the studied compounds.     

Probing the Limits of Selectivity in a Recognition‐Mediated Reaction Network Embedded within a Dynamic Covalent Library

Two recognition‐mediated reaction processes operating through reactive binary complexes drive resolution of a 24‐component dynamic covalent library, assembled from individual aldehydes and nucleophiles. The effectiveness of the library resolution and selective amplification of one recognition‐enabled species over another is limited by the difference in the rates of the recognition‐mediated reactive processes and the strength of the recognition processes employed in the dynamic system.     

Ruthenium tetrazene complexes bearing glucose moieties on their periphery: Synthesis,characterization, and in vitro cytotoxicity

Ruthenium tetrazene complexes with general formula [Cp*RuCl(1,4-R₂N₄)] (Cp* = η⁵-C₅Me₅), where R = benzyl ( 1 ), 2-fluorobenzyl ( 2 ), β-d -glucopyranosyl-unprotected ( 3a ) and acyl-protected ( 3b – d ), 2-acetamido-β-d -glucopyranosyl-unprotected ( 4a ) and acyl-protected ( 4b – d ), propyl-β-d -glucopyranoside-unprotected ( 5a ), and O-acetylated ( 5b ), were synthesized and characterized using nuclear magnetic resonance and electrospray ionization–mass spectrometry. In addition, the molecular structure of 3b was determined using X-ray crystallography. The cytotoxicity of complexes against ovarian (A2780, SK-OV-3) and breast (MDA-MB-231) cancer cell lines and noncancerous cell line HEK-293 was evaluated and compared to cisplatin activity. The carbohydrate-modified complexes bearing acyl-protecting groups exhibited higher efficacy (in low micromolar range) than unprotected ones, where the most active 4d was superior to cisplatin up to five times against all investigated cancer cell lines; however, no significant selectivity was achieved. The complex induced apoptotic cell death at low micromolar concentrations (0.5 μM for A2780 and HEK293; 2 μM for SK-OV-3 and MDA-MB-231).     

Non-equilibrium thermal behaviour of a main chain thermotropic polymer

Abstract

The effect of thermal treatment on the thermodynamic properties and structure of a nematic thermotropic main chain polymer with mesogenic groups containing 3,3′-biphenylene units and octamethylene flexible spacers (BF8) has been studied by DSC and X-ray scattering. We have found that BF8 samples do not crystallize even on very slow cooling from the isotropic state, and possessed a glassy nematic structure at room temperature. The strong influence of the cooling rate on both the enthalpy of the nematic-isotropic transition and the rise of specific heat at the glass transition for BF8 samples was observed. It was attempted to explain this result in terms of the improvement of the nematic structure during cooling.     

Electrochemistry of complex molecular and biomolecular scale entities

Structural mapping of intermediate size and large molecules and biomolecules at ultra-high resolution using single-crystal electrodes and in situ scanning tunnelling microscopy continues to disclose surprising findings. In situ scanning tunnelling spectroscopy has also recently disclosed new electrochemical conductivity features at the level of the single molecule. We overview briefly elements of this development over the last few years, with focus on three recent discoveries: (1) a new packing mode of a core monolayer target thiol, the amino acid cysteine (Cys) on Au(100)-electrodes, quite different from Cys packing on Au(111)- and Au(110)-electrodes; (2) transition of a core ferrocene in situ scanning tunnelling spectroscopy probe from stochastic single-molecule to macroscopic behaviour, a concept at the heart of nanoscience; and (3) unexpected behaviour of the large molybdenum enzyme sulfite oxidase, when going from macroscopic to single-molecule electrochemistry. We compare these studies with other recent discoveries of single-molecule protein conductivity and molecular scale inorganic nanostructures.