A molecular Mo4Bi4 framework composed exclusively of unsupported metal-metal bonds

Reaction of [Cp(2)MoH(2)] with bismuth allyloxide, [Bi{OCH(CH(3))CH==CH(2)}(3)], gave rise to an extended octanuclear complex wherein two cyclic Mo(2)Bi(2) units composed of four Mo-Bi bonds are linked by a Bi-Bi bond. The fact that the construction of such an assembly could be accomplished only in the case of a monomethylation of the parent allyl residue demonstrates a subtle substituent effect.     

Total syntheses of the thiopeptides amythiamicin C and D

The thiopeptides amythiamicin C and D were synthesized by employing amide bond formation, a Stille cross-coupling reaction, and two Negishi cross-coupling reactions as key transformations. The central 2,3,6-trisubstituted pyridine ring of the target compounds was introduced as a 2,6-dibromo-3-iodopyridine, which was selectively metalated at the 3-position and connected to the complete Southern fragment of the amythiamicins by a Negishi cross-coupling. For the synthesis of amythiamicin C, this step was followed by a Negishi cross-coupling at C-6 of the pyridine core. Subsequent attachment of the Eastern fragment was achieved by amide bond formation and macrolactam ring closure by a Stille cross-coupling at C-2. The Eastern bithiazole fragment of the amythiamins was constructed also by regioselective metalation and cross-coupling reactions. The pivotal step involved the diastereoselective addition of 4-bromothiazole-2-magnesium bromide to a chiral sulfinyl imine. For the synthesis of amythiamicin D, the order of cross-coupling at C-6, amide bond formation, and cross-coupling at C-2 was changed. The amide bond formation to the Eastern fragment was performed first and it was subsequently attempted to close the macrolactam by an intramolecular regioselective Stille cross-coupling at C-2. Despite the low regioselectivity of this reaction it paved the way to the immediate completion of the amythiamicin D synthesis when followed by a Negishi cross-coupling at C-6 with 2-zincated methyl thiazole-5-carboxylate.     

Real-time time-dependent density functional theory using density fitting and the continuous fast multipole method

An implementation of real-time time-dependent density functional theory (RT-TDDFT) within the TURBOMOLE program package is reported using Gaussian-type orbitals as basis functions, second and fourth order Magnus propagator, and the self-consistent field as well as the predictor–corrector time integration schemes. The Coulomb contribution to the Kohn–Sham matrix is calculated combining density fitting approximation and the continuous fast multipole method. Performance of the implementation is benchmarked for molecular systems with different sizes and dimensionalities. For linear alkane chains, the wall time for density matrix time propagation step is comparable to the Kohn-Sham (KS) matrix construction. However, for larger two- and three-dimensional molecules, with up to about 5,000 basis functions, the computational effort of RT-TDDFT calculations is dominated by the KS matrix evaluation. In addition, the maximum time step is evaluated using a set of small molecules of different polarities. The photoabsorption spectra of several molecular systems calculated using RT-TDDFT are compared to those obtained using linear response time-dependent density functional theory and coupled cluster methods.     

Cyclic (Alkyl)(Amino)Carbene Complexes of Rhodium and Nickel and Their Steric and Electronic Parameters

N‐heterocyclic carbenes (NHCs) and cyclic (alkyl)(amino)carbenes (CAACs) are of great interest, as their electronic and steric properties provide a unique class of ligands and organocatalysts. Herein, substitution reactions involving novel carbonyl complexes of rhodium and nickel were studied to provide a deeper understanding of the fundamental electronic factors characterizing CAAC^methyl, which were compared with the large array of data available for NHC and sterically more demanding CAAC ligands.     

Emotional voices in context: a neurobiological model of multimodal affective information processing

Just as eyes are often considered a gateway to the soul, the human voice offers a window through which we gain access to our fellow human beings? minds – their attitudes, intentions and feelings. Whether in talking or singing, crying or laughing, sighing or screaming, the sheer sound of a voice communicates a wealth of information that, in turn, may serve the observant listener as valuable guidepost in social interaction. But how do human beings extract information from the tone of a voice? In an attempt to answer this question, the present article reviews empirical evidence detailing the cerebral processes that underlie our ability to decode emotional information from vocal signals. The review will focus primarily on two prominent classes of vocal emotion cues: laughter and speech prosody (i.e. the tone of voice while speaking). Following a brief introduction, behavioral as well as neuroimaging data will be summarized that allows to outline cerebral mechanisms associated with the decoding of emotional voice cues, as well as the influence of various context variables (e.g. co-occurring facial and verbal emotional signals, attention focus, person-specific parameters such as gender and personality) on the respective processes. Building on the presented evidence, a cerebral network model will be introduced that proposes a differential contribution of various cortical and subcortical brain structures to the processing of emotional voice signals both in isolation and in context of accompanying (facial and verbal) emotional cues.     

Proteome and phosphoproteome of primary cultured pig urothelial cells

Epithelial tissue lining the inner side of the urinary bladder is the most common target for bladder cancer-related diseases. Bladders of freshly slaughtered pigs were utilised for a comprehensive analysis of the proteome and phosphoproteome of bladder epithelial cells. Following protein separation by 2-D gel electrophoresis and identification by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOF-MS) the first proteome and phosphoproteome maps of pig urinary bladder epithelial cells (PUBEC) were established. A total of 120 selected protein spots were identified. By using the La(3+) enrichment method further developed in our laboratory we identified 31 phosphoproteins with minimal contamination by non-phosphopeptides. The 2-DE map of pig urothelial cells may prove as a useful tool for studies on uroepithelial biology, and the analysed phosphoproteins expression pattern, together with the whole cell proteome, will be helpful for identifying the proteins involved in bladder-related diseases.