Neuromagnetic brain responses to words from semantic sub- and supercategories

Background  

We explored spatio-temporal patterns of cortical activity evoked by written words from super-ordinate and sub-ordinate semantic categories and hoped to find a differential cortical and/or temporal distribution of the brain response depending on the level of the categories. Twenty-three subjects saw 360 words belonging to six sub-ordinate categories (mammals, birds, fish, fruit, flowers, trees) within two super-ordinate categories (fauna, flora). Visually evoked magnetic fields were determined from whole-head (148-sensor) magnetoencephalography and analyzed in the source space (Minimum Norm Estimate).     

Synthesis, linear, and quadratic-nonlinear optical properties of octupolar D3 and D2d bipyridyl metal complexes

A series of D3 (Fe(II), Ru(II), Zn(II), Hg(II)) and D2d (Cu(I), Ag(I), Zn(II)) octupolar metal complexes featuring different functionalized bipyridyl ligands has been synthesized, and their thermal, linear (absorption and emission), and nonlinear optical (NLO) properties were determined. Their quadratic NLO susceptibilities were determined by harmonic light scattering at 1.91 microm, and the molecular hyperpolarizability (beta0) values are in the range of 200-657 x 10(-30) esu for octahedral complexes and 70-157 x 10(-30) esu for tetrahedral complexes. The octahedral zinc(II) complex 1 e, which contains a 4,4'-oligophenylenevinylene-functionalized 2,2'-bipyridine, exhibits the highest quadratic hyperpolarizability ever reported for an octupolar derivative (lambdamax=482 nm, beta1.91(1 e)=870 x 10(-30) esu, beta0(1 e)=657 x 10(-30) esu). Herein, we demonstrate that the optical and nonlinear optical (NLO) properties are strongly influenced by the symmetry of the complexes, the nature of the ligands (donor endgroups and pi linkers), and the nature of the metallic centers. For example, the length of the pi-conjugated backbone, the Lewis acidity of the metal ion, and the increase of ligand-to-metal ratio result in a substantial enhancement of beta. The contribution of the metal-to-ligand (MLCT) transition to the molecular hyperpolarizability is also discussed with respect to octahedral d6 complexes (M=Fe, Ru).     

Thiophosphorylated cavitand: structure and affinity towards soft metal ions

The iiii stereoisomer of the tetrathiophosphonate-calix[4]resorcinarene host 1 exhibited excellent extraction properties towards soft metal ions, with a better affinity for Ag⁺ (91%), than for Tl⁺ (38%) and Hg²⁺ (16%). The extraction of other picrate salts (Cu²⁺, Ni²⁺, Co²⁺, Zn²⁺, Cd²⁺, Pb²⁺) was not detected. The stoichiometry and the structure of the Hg²⁺, Tl⁺ and Ag⁺ complexes were studied by NMR in solution and gave respectively 1:1, 1:1 and 1:2 host-guest complexes. The formation of the self-assembled 1₂·(AgPic)₄ complex was independent on the anion and only observed with silver(I) ion.     

A combinatorial approach toward the generation of ambiphilic peptide-based inhibitors of protein:geranylgeranyl transferase-1

A combinatorial synthesis of oligopeptide analogues and their evaluation as protein:geranylgeranyl transferase inhibitors is presented. The combinatorial strategy is based on the random mutation, in each new generation, of one of any of the four amino acid building blocks of which the most effective compounds of the previous generation are assembled. In this way, a progressive improvement of the average inhibitory activity was observed until the fifth generation. The most active inhibitors were found to inhibit PGGT-1 in the low micromolar range (IC(50): 3.8-8.1 microM).     

Properties and applications of precision oligomer materials; where organic and polymer chemistry join forces

Precise oligomeric materials constitute a growing area of research with implications for various applications as well as fundamental studies. Notably, this field of science which can be termed macro-organic chemistry, draws inspiration from both traditional polymer chemistry and organic synthesis, combining the molecular precision of organic chemistry with the materials properties of macromolecules. Discrete oligomers enable access to unprecedented materials properties, for example, in self-assembled structures, crystallization, or optical properties. The degree of control over oligomer structures resembles many biological systems and enables the design of materials with tailored properties and the development of fundamental structure–property relationships. This Review highlights recent developments in macro-organic chemistry from synthetic concepts to materials properties, with a focus on self-assembly and molecular recognition. Finally, an outlook for future research directions is provided.     

A simple ionic triphenylene receptor for catecholamines, serotonin and D-glucosamine in buffered water

The combination of hydrophobic effects and ionic pairing within a triphenylene-based receptor were exploited for the binding of biological phenylethylamines, serotonin and D-glucosamine in phosphate buffered water.     

Generation of C6H4+* by laser vaporization of magnesium with o-C6H4F2 in argon carrier gas

A route to efficient generation of C6H4+*, potentially the benzyne radical cation, is presented. Laser vaporization of Mg+* and supersonic expansion in helium doped with o-, m-, or p-C6H4F2 yields, among other ions, o-, m-, p-C6H4F2Mg+* complexes, but no C6H4+*. Collision-induced dissociation experiments show that the o-C6H4F2Mg+* complex can be converted into C6H4+* in a mildly energetic collision, with a center-of-mass energy around 1-2 eV. These conditions can also be reached in the ion source when argon is used as a carrier gas. In this way, mass spectra containing the desired m/z 76 peak, i.e. C6H4+*, are obtained.