Synthesis of diisocyanides with phenolic groups and their polymerization to helically chiral poly(quinoxaline‐2,3‐diyl)s

The development of synthetic routes which lead to five new diisocyanide monomers with one or two phenolic groups is described. Their polymerization behavior is studied with Pd‐ and Ni‐based initiators, as well as under microwave irradiation. The polymerizability is mainly dominated by steric effects as is concluded from experiments using different protecting groups. Chiroptical properties of these new polymers are studied by CD‐spectroscopy. After deprotection, helically chiral poly(quinoxalin‐2,3‐diyl)s are obtained which display a Brønsted function attached to a stereolabile biaryl axis whose configuration should be influenced by the chiral polymer backbone. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1320–1329     

A Pilot Survey of Vocal Health in Young Singers

The objective of this study was to determine the incidence of vocal problems in young choir singers and to correlate vocal problems with demographic and behavioral information. A questionnaire addressing vocal habits and hygiene was offered to 571 young choir singers, up to 25 years of age, who sing at least weekly; 129 (22.6%) responded. More than one-half of the respondents had experienced vocal difficulty, particularly older adolescents. Detrimental behaviors and circumstances surveyed were not reflective of the incidence of vocal difficulty, except for morning hoarseness, chronic fatigue, insomnia, and female gender after puberty. Voice care professionals should be aware that self-reported voice difficulties are common among young choral singers, especially postpubescent girls, and children with symptoms consistent with reflux (morning hoarseness) and emotional stress (insomnia). Laryngologists should communicate with choral conductors and singing teachers to enhance early identification and treatment of children with voice complaints, and to develop choral educational strategies that help decrease their incidence.     

Versuche zur Totalsynthese von Brefeldin A

Preliminary results leading towards the total synthesis of Brefeldin A are presented.     

Beiträge zur Chemie des Phosphors. 203 [1].(t- BuSi)4P3Cl3, das erste Silaphosphan mit Norcuban-Struktur

Contributions to the Chemistry of Phosphorus. 203. (t-BuSi)₄P₃Cl₃ – The First Silaphosphane with a Structure Analogous to Norcubane The reaction of t-BuSiCl₃ with LiAl(PH₂)₄ yields the compound (t-BuSi)₄P₃Cl₃ ( 1 ), which has been isolated in pure form. According to NMR spectroscopic investigations and an X-ray single-crystal analysis, 1 is 2,4,6,7-tetra-tert-butyl-2,4,7-trichloro-1,3,5-triphospha-2,4,6,7-tetrasilatricyclo[3.1.1.0^3,6]heptane and thus the first silaphosphane with a structure analogous to norcubane. The compound crystallizes monoclinically in the space group P2₁/n with a = 1102.1 pm, b = 1609.2 pm, c = 1612.8 pm, β = 90.90° and Z = 4. The main structural feature is a cube alternately composed of Si and P, from which one phosphorus atom has been removed. The Si atoms are each substituted by t-Bu groups, the three adjacent to the missing corner additionally by Cl atoms.     

Der Gaskomplex MnAlF5 und sein Einfluß auf die sublimative Reinigung von AlF3

The Gas Complex MnAlF₅ and its Influence on the Purification of AlF₃ by Sublimation The gas complex MnAlF₅ has been determined mass spectroscopically by the ions MnAlF₅⁺ and MnAlF₄⁺. The gas complex MnAlF₅ is formed above 973 K by heating up mixtures of AlF₃/MnF₂ or AlF₃ · 3 H₂O endowed with Mn²⁺ or by heating up solid MnAlF₅ too. At 1 008 K the enthalpie of dissociation is 197 kJ/mole. The equilibrium structures of the high spin molecule MnAlF₅ (S = 5/2) were examined with ab initio calculations at the HF-level by comlete gradient optimizing. Two minimum structures were found on the potential energy surface. A bidentate fluorine bridged structure was found to be the most stable at the HF-level. Vibrational frequencies and thermodynamic functions of complex formation were estimated for both minimum structures. The importance of the formation of the gas complex for the separation of MnF₂ and AlF₃ by sublimation is discussed.