From Eight‐Membered 10π Electron Sulfur–Nitrogen Cycles to Bicycles and Cages: A Theoretical Approach

A simple way of rationalizing the structures of cyclic, bicyclic, and tricyclic sulfur–nitrogen species and their congeners is presented. Starting from a planar tetrasulfur tetranitride with 12π electrons, we formally derived on paper a number of heterocyclic eight‐membered 10π electron species by reacting the 3p orbitals of two opposite sulfur centers with one radical each, or by replacing these centers by other atoms with five (P) or four (Si, C) valence electrons. This led to planar aromatic 10π electron systems, nonplanar bicyclic structures with a transannular S?S bond, and tricyclic structures by bridging the planar rings with an acceptor or donor unit. The final structures depend on the number of π electrons in the bridges. Intermediate biradicals are stabilized by Jahn–Teller distortion, giving transannular S?S bonds between the NSN units. This procedure may be summarized by two rules, which provide a rationale for the structures of a large number of sulfur–nitrogen‐based molecules. The long bonds between the NSN units show a p character of >95 %. The qualitative results have been compared with known molecular structures and the results of B3LYP/cc‐pVTZ calculations as well as CASSCF and CASVB calculations. B3LYP/cc‐pVTZ calculations have also provided the UV/Vis spectra and the NICS values of the planar 10π systems.     

Quantitative monitoring of yeast fermentation using Raman spectroscopy

Compared to traditional IR methods, Raman spectroscopy has the advantage of only minimal interference from water when measuring aqueous samples, which makes this method potentially useful for in situ monitoring of important industrial bioprocesses. This study demonstrates real-time monitoring of a Saccharomyces cerevisiae fermentation process using a Raman spectroscopy instrument equipped with a robust sapphire ball probe. A method was developed to correct the Raman signal for the attenuation caused by light scattering cell particulate, hence enabling quantification of reaction components and possibly measurement of yeast cell concentrations. Extinction of Raman intensities to more than 50 % during fermentation was normalized with approximated extinction expressions using Raman signal of water around 1,627 cm^?1 as internal standard to correct for the effect of scattering. Complicated standard multi-variant chemometric techniques, such as PLS, were avoided in the quantification model, as an attempt to keep the monitoring method as simple as possible and still get satisfactory estimations. Instead, estimations were made with a two-step approach, where initial scattering correction of attenuated signals was followed by linear regression. In situ quantification measurements of the fermentation resulted in root mean square errors of prediction (RMSEP) of 2.357, 1.611, and 0.633 g/L for glucose, ethanol, and yeast concentrations, respectively.     

A New Route to 6-Aryl-substituted 3,4-Dihydronaphthalene Derivatives via Pd (O)-Catalyzed Cross-Coupling Reaction of Aryl Zinc Chlorides with an Aryl Triflate

A procedure for the Pd (O)-catalyzed cross coupling of the triflate of 6-hydroxy-3,4-dihydronaphthalene-2-methylcarboxylate with various aryl zinc chlorides was developed, which represents an efficient approach to 6-aryl-substituted naphthalene derivatives.     

The Improved Preparation of 7,8-Dihydro-Quinoline-5(6H)-One and 6,7-Dihydro-5H-1-Pyrindin-5-one

Compounds 7,8-dihydroquinoline-5(6H)-one (3) and 6,7-dihydro-5H-1-pyrindin-5-one (5) are formed by new methods from 1,3-diketone compound, ammonium acetate and 1,1,3,3-tetraethoxylpropane.

     

Relationship between changes in voice pitch and loudness

Changes in mean fundamental frequency accompanying changes in loudness of phonation are analyzed in 9 professional singers, 9 nonsingers, and 10 male and 10 female patients suffering from vocal functional dysfunction. The subjects read discursive texts with noise in earphones, and some also at voluntarily varied vocal loudness. The healthy subjects phonated as softly and as loudly as possible at various fundamental frequencies throughout their pitch ranges, and the resulting mean phonetograms are compared. Mean pitch was found to increase by about half-semitones per decibel sound level. Grossly, the subject groups gave similar results, although the singers changed voice pitch more than the nonsingers. The voice pitch changes may be explained as passive results of changes of subglottal pressure required for the sound level variation.     

Magnetic Properties of TlCo2Se2 Studied by Mössbauer Spectroscopy

Hyperfine Interactions - The quasi two-dimensional antiferromagnetic compound TlCo2Se2 has been studied by 57Fe Mössbauer spectroscopy. Small single crystals have been made with 2% Fe doping....     

The lagrange multiplier rule for multi-dimensional problems of optimal control

In this paper a modified form of Pontryagin's maximum principle is developed, which also holds for problems of optimal control with respect to functions of several independent variables.