Expanded Mercaptocalixarenes: A New Kind of Macrocyclic Ligands for Stabilization of Polynuclear Thiolate Clusters

The syntheses and properties of expanded 4-tert-butyl-mercaptocalix[4]arenes, in which the methylene linkers are replaced by −CH₂NRCH₂− or −CH₂NRCH₂− and −CH₂NRCH₂CH₂CH₂NRCH₂− units, are described. The new macrocycles were obtained in a step-wise manner, utilizing fully protected, i. e. S-alkylated, derivatives of the oxidation-sensitive thiophenols in the cyclisation steps. Reductive cleavage of the macrobicyclic or macrotricyclic intermediates ( 6 , 7 , 11 ) afforded the free thiophenols (H₄ 8 , H₄ 9 , and H₄ 12 ) in preparative yields as their hydrochloride salts. The protected proligands can exist in two conformations, resembling the “cone” and “1,3-alternate” conformations found for the parent calix[4]arenes. The free macrocycles do not show conformational isomerism, but are readily oxidized forming intramolecular disulfide linkages. Preliminary complexation experiments show that these expanded mercaptocalixarenes can serve as supporting ligands for tetranuclear thiolato clusters.     

Heritability of Stroop and flanker performance in 12-year old children

Background  

There is great interest in appropriate phenotypes that serve as indicator of genetically transmitted frontal (dys)function, such as ADHD. Here we investigate the ability to deal with response conflict, and we ask to what extent performance variation on response interference tasks is caused by genetic variation. We tested a large sample of 12-year old monozygotic and dizygotic twins on two well-known and closely related response interference tasks; the color Stroop task and the Eriksen flanker task. Using structural equation modelling we assessed the heritability of several performance indices derived from those tasks.     

Simultaneous freezing of chirality and in-out conformation of a macropentacyclic cryptand by protonation

Compound 1, a cryptand-derived macropentacycle, is a flexible molecule that encompasses many conformations (symmetrical, unsymmetrical, and chiral ones) depending on the observation temperature (VT 1H NMR). Selective monoprotonation of this molecule leads to a totally unsymmetrical, rigidly chiral species in solution (1H NMR). Helical chirality and in-out conformation of monoprotonated 1 are observed in the solid state by X-ray diffraction analysis, as well as the proton location. The latter is bound to the endo bridgehead nitrogen atom and involved in hydrogen-bonding interactions with the three closest sulfurs. Significant induction of chirality is triggered by reaction of 1 with the optically active (R)-(-)-1,1'-binaphthyl-2,2'-diylphosphoric acid. It proceeds with a maximum 24% diastereomeric excess, as shown by the splitting, in the 62:38 intensity ratio, of several 1H NMR signals. These correspond to the two indistinguishable diastereomeric ion pairs: (Lambda-[1-H])((R)-(-)-BNP) and (Delta-[1-H])((R)-(-)-BNP).     

The contribution of high frequencies to human brain activity underlying horizontal localization of natural spatial sounds

Background  

In the field of auditory neuroscience, much research has focused on the neural processes underlying human sound localization. A recent magnetoencephalography (MEG) study investigated localization-related brain activity by measuring the N1m event-related response originating in the auditory cortex. It was found that the dynamic range of the right-hemispheric N1m response, defined as the mean difference in response magnitude between contralateral and ipsilateral stimulation, reflects cortical activity related to the discrimination of horizontal sound direction. Interestingly, the results also suggested that the presence of realistic spectral information within horizontally located spatial sounds resulted in a larger right-hemispheric N1m dynamic range. Spectral cues being predominant at high frequencies, the present study further investigated the issue by removing frequencies from the spatial stimuli with low-pass filtering. This resulted in a stepwise elimination of direction-specific spectral information. Interaural time and level differences were kept constant. The original, unfiltered stimuli were broadband noise signals presented from five frontal horizontal directions and binaurally recorded for eight human subjects with miniature microphones placed in each subject's ear canals. Stimuli were presented to the subjects during MEG registration and in a behavioral listening experiment.     

Fifty Years of Inorganic Biomimetic Chemistry: From the Complexation of Single Metal Cations to Polynuclear Metal Complexes by Multidentate Thiolate Ligands

This article covers 50 years of coordination chemistry of transition metal complexes and metal-sulfur aggregates involving thiolate-incorporating ligands by reviewing selected examples. The studies in the coordination chemistry of sulfur-rich ligands have been undoubtedly triggered and fed by the concomitant development of bioinorganic chemistry, particularly of iron-sulfur enzymes. The review is broken down in five sections, which examine complexes of increasing nuclearity, including binuclear complexes based on compartmental macrocyclic ligands. We show also how ligand engineering has allowed the researchers in the field to control the nuclearity of the complexes, which was a particularly difficult task for sulfur-based ligands, as thiolates show a strong tendency to coordinate to more than one metal cation at once.