A facile synthesis of 1,1-bis(silyl)ethenes

Symmetrical 1,1-bis(silyl)ethenes have been easily prepared via ruthenium complex-catalyzed silylative coupling cyclization of 1,2-bis(dimethylvinylsiloxy)ethane to give 2,2,4,4-tetramethyl-3-methylene-1,5-dioxa-2,4-disilacycloheptane with excellent selectivity and good yield, followed by its reaction with Grignard reagents. The cyclic product can also be effectively transformed into cyclic carbosiloxane, 2,2,4,4,6,6,8,8-octamethyl-3,7-dimethylene-1,5-dioxa-2,4,6,8-tetrasilacyclooctane.     

Master equation simulations of bistable and excitable dynamics in a model of a thermochemical system

The effect of fluctuations on the dynamics of a model of a bistable thermochemical system is studied by means of the master equation. The system has three stationary states and exhibits two types of bistability: the coexistence of two stable focuses and the coexistence of a stable focus with a stable limit cycle separated by a saddle point. Stochastic effects are important when the system is close to the bifurcation, in which the stable limit cycle disappears through a homoclinic orbit. In this case the distribution of the first passage time from the stable limit cycle to the stable focus has a multipeak form. The dependence of this distribution on the number of particles is presented. Near the homoclinic orbit bifurcation, the system also exhibits excitability due to a particular shape of the basin of attraction of the stable focus.     

New catalytic route to functionalized vinylboronates

Vinylsubstituted boronates i.e. vinyldioxaborolane and vinyldioxaborinane react regioselectively with olefins in the presence of RuHCl(CO)(PCy3)2 with the formation of functionalized vinylboron derivatives. The reaction opens a new catalytic route for preparation of organoboranes.     

Optisches Drehungsvermögen und Konformation, 3. Mitt.: Über die Verhältnisse beicis-Ringschlußreaktionen epimerer Aminoalkohole der Ephedrinreihe

Zusammenfassung (–)-Norephedrin, (–)-Ephedrin d. h.d _g-erythro-1-Phenyl-2-amino-bzw.-methylamino-propanole und deren rechtsdrehendethreo-Diastereomeren wurden durch Phosgen bzw. Chloracetylchlorid in die entsprechenden Oxazolidon-(2)- und Morpholon-(5)-Derivate umgewandelt. Die 3,4-Dimethyl-2-phenyl-morpholone wurden danach mit LiAlH₄ zu Morpholinderivaten reduziert. Der Unterschied zwischen dem Drehwert eineserythro--Aminoalkohols und irgendeines seiner cyclischen Derivate ist jeweils größer als in derthreo-Reihe. Das kann auf die größere Gesamtänderung in der Konformationsasymmetrie bei den Umwandlungen dererythro-Isomeren zurückgeführt werden. An Hand derBrewster-Methode waren Aussagen nur über die bevorzugten Konformationen der genannten sechsgliedrigen cyclischen Verbindungen möglich.Mit 2 Abbildungen.Herrn Prof. Dr.F. Wessely freundlichst zum 70. Geburtstag gewidmet.     

Excitation spectrum and thermodynamics of domain walls in the biaxial ferromagnet

The problem on spectrum of linear excitations in the presence of a moving domain wall in 1D Heisenberg ferromagnet with orthorhombic anisotropy is exactly solved. The explicit expressions for spin waves scattering on the domain wall are obtained. The phase shift of a spin wave, as the result of collision of spin wave with a moving wall, is exactly determined. The change in magnon density of states is calculated from this scattering data, and the contribution of domain walls to the classical low-temperature thermodynamics is found.     

Ultrasonic processing of dairy systems in large scale reactors

High intensity low frequency ultrasound was used to process dairy ingredients to improve functional properties. Based on a number of lab-scale experiments, several experimental parameters were optimised for processing large volumes of whey and casein-based dairy systems in pilot scale ultrasonic reactors. A continuous sonication process at 20 kHz capable of delivering up to 4 kW of power with a flow-through reactor design was used to treat dairy ingredients at flow rates ranging from 200 to 6000 mL/min. Dairy ingredients treated by ultrasound included reconstituted whey protein concentrate (WPC), whey protein and milk protein retentates and calcium caseinate. The sonication of solutions with a contact time of less than 1 min and up to 2.4 min led to a significant reduction in the viscosity of materials containing 18% to 54% (w/w) solids. The viscosity of aqueous dairy ingredients treated with ultrasound was reduced by between 6% and 50% depending greatly on the composition, processing history, acoustic power and contact time. A notable improvement in the gel strength of sonicated and heat coagulated dairy systems was also observed. When sonication was combined with a pre-heat treatment of 80 °C for 1 min or 85 °C for 30 s, the heat stability of the dairy ingredients containing whey proteins was significantly improved. The effect of sonication was attributed mainly to physical forces generated through acoustic cavitation as supported by particle size reduction in response to sonication. As a result, the gelling properties and heat stability aspects of sonicated dairy ingredients were maintained after spray drying and reconstitution. Overall, the sonication procedure for processing dairy systems may be used to improve process efficiency, improve throughput and develop value added ingredients with the potential to deliver economical benefits to the dairy industry.     

Reversible formation of glassy water in slowly cooling diluted drops

This letter presents experimental results obtained with a differential scanning calorimeter (DSC), which indicate that glassy water can be produced reversibly within slowly cooling diluted H2SO4/H2O drops.