Synthese und chemie von 4R-silacyclohexa-2,5-dienen und 4R-silacyclohexa-2,4-dienen

The 1(Z),4(Z)-1,5-dilithium-3R-3-methoxypenta-1,4-dienes, available by cleavage of 1,1-di-n-butyl-4R-4-methoxy-1-stannacyclohexane-2,5-dienes with n-BuLi in ether, react with dichlorosilanes (R′R″ SiCl₂; R′, R″ = H, alkyl, aryl, alkoxy) to give 1R′,1R″,4R-4-methoxy-1-silacyclohexa-2,5-dienes.Claevage of the ether group with BBr₃, BCl₃ or PCl₃ gives 6-chloro(bromo)-1-silacyclohexa-2,4-dienes or 1,5-dichloro-1-silacyclohexane-2,4-dienes, respectively.Ether cleavage of 4R-4-methoxy-1-silacyclohexa-2,5-dienes with sodium results in the formation of 4R-1-silacyclohexadienyl anions, which can be hydrolyzed to give 1-silacyclohexa-2,4-dienes which reach further with trichloromethylsilane to give 6-trimethylsilyl-1-silacyclohexa-2,4-dienes.Phase transfer-catalyzed conversion of 1-chlorosilacyclohexadienes into the fluoro derivatives as well as further substitution reactions of 1-chlorosilacyclohexadienes are described.The ¹H NMR, ¹³C NMR, IR and mass spectra of the silacyclohexadienes are discussed.     

Structure and thermal stability of MOCVD ZrO2 films on Si (1 0 0)

The structure and thermal stability of ZrO₂ films grown on Si (1 0 0) substrates by metalorganic chemical vapor deposition have been studied by high-resolution transmission electron microscopy, selected area electron diffraction and X-ray energy dispersive spectroscopy. As-deposited films consist of tetragonal ZrO₂ nanocrystallites and an amorphous Zr silicate interfacial layer. After annealing at 850°C, some monoclinic phase is formed, and the grain size is increased. Annealing a 6 nm thick film at 850°C in O₂ revealed that the growth of the interfacial layer is at the expense of the ZrO₂ layer. In a 3.0 nm thick Zr silicate interfacial layer, there is a 0.9 nm Zr-free SiO₂ region right above the Si substrate. These observations suggest that oxygen reacted with the Si substrate to grow SiO₂, and SiO₂ reacted with ZrO₂ to form a Zr silicate interfacial layer during the deposition and annealing. Oxygen diffusion through the tetragonal ZrO₂ phase was found to be relatively easier than through the monoclinic phase.     

Determination of polybutylene terephthalate polycondensation equilibrium constant using a batch reactor

The PBT polycondensation equilibrium constant at 255°C was determined using a batch reactor. Starting from a Polybutylene terephthalate (PBT) prepolymer having a degree of polymerisation of 12.7, equilibrium experiments were performed in the range of 1 to 50 mbar. The equilibrium degree of polymerisation (i) was determined indirectly using dilute solution viscometry of a solution of 1 weight % PBT in m - cresol. The degree of polymerisation of PBT obtained at equilibrium in the range of 1 to 50 mbar at 255°C as a function of the BDO partial pressure (mbar) could be expressed by: i = 111.47 − 86.18 exp(−1.14 equation/tex2gif-stack-1.gif). The equilibrium solubility of 1,4 butanediol (BDO) in the PBT melt was derived form the BDO partial pressure using the Flory - Huggins theory. The PBT polycondensation reaction equilibrium constant was related to the degree of polymerisation by the equation: in the range i = 26 − 100. The PBT polycondensation equilibrium constant at high degrees of polymerisation is in line with literature data and thermodynamics.     

INDUCTION and DISAPPEARANCE OF THYMINE DIMERS IN HUMAN SKIN EXPOSED TO UVB RADIATION: FLOW CYTOMETRIC MEASUREMENTS IN REPLICATING and NONREPLICATING EPIDERMAL CELLS

We have earlier reported on determining UV-induced DNA damage in murine epidermal cell suspensions by flow cytometric analysis of the fluorescence from a fluorescein isothiocyanate-labeled antibody (H3) directed against thymine dimers (T>2-M-phase cells can further be distinguished from cell doublets by pulse-shape discrimination. Thus, T>(i.e. G₀-G₁, S or G₂-M phases) can be determined after in vivo exposure of human skin to environmentally relevant UVB (280–315nm) doses. The method was applied to measure the decrease of T>0-G₁ phase) and replicating cells (S phase or G₂-M phase) from seven volunteers exposed to twice their minimal erythema dose. The reduction in the average T>0-G₁ cells and 70% (ranging between 37% and 100%) for the S + G₂-M cells. The difference was statistically highly significant. Determination of individual DNA repair capacities with this method can become a convenient diagnostic tool for patients with DNA repair disorders, or it may even be used to identify individuals with low repair proficiencies and increased risk of developing skin cancers.     

On the implementation of symmetric and antisymmetric periodic boundary conditions for incompressible flow

In this paper we consider symmetric and antisymmetric periodic boundary conditions for flows governed by the incompressible Navier-Stokes equations. Classical periodic boundary conditions are studied as well as symmetric and antisymmetric periodic boundary conditions in which there is a pressure difference between inlet and outlet. The implementation of this type of boundary conditions in a finite element code using the penalty function formulation is treated and also the implementation in a finite volume code based on pressure correction. The methods are demonstrated by computation of a flow through a staggered tube bundle.     

Elementary Properties of the Finite Ranks

This note investigates the class of finite initial segments of the cumulative hierarchy of pure sets. We show that this class is first-order definable over the class of finite directed graphs and that this class admits a first-order definable global linear order. We apply this last result to show that FO(<, BIT) = FO(BIT).     

Structural comparison of gadolinium and lanthanum silicate films on Si(1 0 0) by HRTEM, EELS and SAED

High-resolution transmission electron microscopy (HRTEM), electron energy loss spectroscopy (EELS) and selected area electron diffraction (SAED) were used to study gadolinium and lanthanum silicate films deposited on Si(1 0 0) substrates using electron-beam evaporation from pressed-powder targets. As-deposited films consist of an amorphous silicate layer without an interfacial layer. After annealing at 900 °C in oxygen for 2 min, an interfacial SiO₂ layer is formed in the gadolinium silicate film, while this interfacial layer is a SiO₂-rich lanthanum silicate layer in the lanthanum silicate film. The formation of interfacial silicate layers is thermodynamically more favorable for the lanthanum films than for the gadolinium films. The gadolinium silicate films crystallize at a temperature between 1000 and 1050 °C, while the crystallization temperature for the lanthanum silicate films is between 900 and 950 °C.     

Propellanes—LIII : The -ene reaction of olefinic propellanes with singlet oxygen

The -ene reactions of propellanes containing an anhydride ring or a methylimide ring undergo secondary orbital control. In attack by ¹O₂ only the syn-products are obtained. In the corresponding lactone or ether steric hindrance plays a more important role in the direction of attack.