N-Functionalised heterocyclic dicarbene complexes of silver: Synthesis and structural studies

A range of new diimidazolium salts, held together by an alkyl unit and bearing alcohol pendant arms on their nitrogen, was synthesized. A short modular reaction pathway leads to the N-heterocyclic carbene (NHC) precursors, differing by the flexibility of the bridge, the steric bulk of substituents in α-position of the OH groups and the anions. Treatment of diimidazolium salts with Ag₂O yields Ag^I(carbene)₂ complexes. The related trimethylene-bridged bis-NHC silver complexes 6 and 7 were crystallised with di-tosylate and di-hexafluorophosphate anions, respectively. Their X-ray structures revealed dimeric species, involving two ligands with different arrangements around the Ag cations, leading to crossed and parallel conformations.     

Intramolecular "hydroiminiumation and -amidiniumation" of alkenes: a convenient, flexible, and scalable route to cyclic iminium and imidazolinium salts

Addition of a stoichiometric amount of HCl to alkenylaldimines, -formamidines, and -amidines results in the protonation of the sp2-nitrogen atom. The resulting alkenylaldiminium, -formamidinium, and -amidinium salts can be isolated and fully characterized, including single-crystal X-ray diffraction studies. Heating solutions of these salts induces ring closure cleanly and regioselectively via formal "exo" addition of the nitrogen-hydrogen bond to the pendent carbon-carbon double bond, affording the corresponding cyclic aldiminium, dihydroisoquinolinium, and imidazolinium salts. Of special interest, novel 4,4-disubstituted imidazolinium salts are accessible via this synthetic route. Similarly, addition of phosgene to alkenyl ureas and alkenyl amides, followed by gentle heating, cleanly affords C-chloro imidazolinium, and cyclic C-chloro iminium salts, respectively. Treatment of the latter with tetrakis(triphenylphosphine)palladium allows for the preparation of the first transition-metal complex bearing a cyclic arylaminocarbene as ligand. Deuterium labeling experiments suggest that the mechanism of the hydroiminiumation and -amidiniumation reactions involves an intramolecular proton transfer to the double bond in the rate-determining step. This novel synthetic methodology gives access to a variety of N-heterocyclic carbene (NHC) and cyclic alkyl- and arylaminocarbene (CAAC) precursors.     

Design and synthesis of an array of selective androgen receptor modulators

We describe the design, using shape comparison and fast docking computer algorithms, and rapid parallel synthesis of a 1300 member array based on GSK7721, a 4-aminobenzonitrile androgen receptor (AR) antagonist identified by focused screening of the GSK compound collection. The array yielded 352 submicromolar and 17 subnanomolar AR agonists as measured by a cell-based reporter gene functional assay. The rapid synthesis of a large number of active compounds provided valuable information in the optimization of AR modulators, which may be useful in treating androgen deficiency in aging males.     

Ising phases of Heisenberg ladders in a magnetic field

We show that Dzyaloshinskii-Moriya (DM) interactions can substantially modify the phase diagram of spin-1/2 Heisenberg ladders in a magnetic field provided they compete with exchange. For nonfrustrated ladders, they induce a local magnetization along the DM vector that turns the gapless intermediate phase into an Ising phase with broken translational symmetry, while for frustrated ladders, they extend the Ising order of the half-integer plateau to the surrounding gapless phases of the purely Heisenberg case. Implications for experimental ladder and dimer systems are discussed.     

Colloid particles in the interaction field of a disclination line in a nematic phase

On the basis of linear hydrodynamics, we analyze the trajectory of particle-hedgehog systems, attracted by a -1/2 disclination (defect line) in a nematic liquid crystal. We show that, as with the interactions between like-particles, the interaction between a particle and a disclination has an electrostatic analogue, the splay replacing the electric field, except for the symmetry properties. The disclination thus attracts the beads along nonradial tracks and in a self-assembling process, or template mechanism, may build a microscopic necklace with them.     

Improving the adhesion of polymethacrylate thin films onto indium tin oxide electrodes using a silane-based “Molecular Adhesive”

Indium tin oxide (ITO) is the most commonly used transparent conducting substance. It has been used in numerous applications such as light-emitting diodes. In most applications and studies, the ITO surface is further coated with additional layers. The interface between the ITO and the coating is of utmost importance since it affects the physical and chemical properties of the final device. Improving the adhesion between ITO and a coating layer can be achieved by applying a “molecular adhesive” as an inter-phasing molecular layer. In this study, we used 3-(trimethoxysilyl)propyl methacrylate as a “molecule adhesive” for better connection between ITO and a polymethacrylate layer. The samples were studied by electrochemistry, contact angle goniometry, atomic force microscopy, and nano scratch microscopy. These studies clearly show that a simple silanization process formed a thin molecular adhesive layer, which did not influence the physical and chemical properties of the final coated electrode and at the same time increased significantly the adhesion between the ITO and the polymethacrylate coating.

     

Testing copositivity with the help of difference-of-convex optimization

We consider the problem of minimizing an indefinite quadratic form over the nonnegative orthant, or equivalently, the problem of deciding whether a symmetric matrix is copositive. We formulate the problem as a difference of convex functions problem. Using conjugate duality, we show that there is a one-to-one correspondence between their respective critical points and minima. We then apply a subgradient algorithm to approximate those critical points and obtain an efficient heuristic to verify non-copositivity of a matrix.