Novel liquid crystals based on [1]benzothieno[3,2- b ][1]benzothiophene

Four series of new [1]benzothieno[3,2- b ][1]benzothiophene derivatives have been synthesized. In the non-chiral series a SmA phase occurs, while the chiral series exhibits a rather wide antiferroelectric SmC * A phase just below the SmA phase. The SmA-SmC * A phase transition has been studied using DSC and dielectric spectroscopy. In the SmC * A phase the spontaneous quantities have been measured. The tilt angle shows a typical temperature dependence and the values of spontaneous polarization are rather moderate. The length of the helical pitch increases on increasing the length of the non-chiral alkyl chain.     

Resonance method for IR sensing

A highly sensitive method for infrared radiation detection based on thermal resonance in an active bolometer is set forth. An active bolometer is a self-oscillating system consisting of an IR-sensitive cell in a feedback circuit of an adjustable proportional controller. The analysis of an active bolometer autonomous (dark) dynamics reveals that with a generalized gain factor A variation the system evolves from relaxation type towards oscillating and self-oscillating type. When A=A_c, where A_c is a critical value of the generalized gain factor A, the steady state loses stability through self-excited thermal oscillations. The resonance in a system weakly perturbed by IR radiation modulated at self-oscillation frequency q₀[1+exp(iω_ct)] is considered. It is shown that in a small precritical vicinity =(A−A_c)/A_c of the gain factor the amplitude of forced thermal oscillations is proportional to q₀/A_c. The D^* calculation reveals that the detection power of a passive (A=0) bolometer increases with feedback introduction by a factor of 1/||. The detection powers of feasible versions of an active bolometer are compared.     

Aufbau und Zunderverhalten von Niob-Bor-Silicium-Legierungen

Zusammenfassung Der Aufbau des Dreistoffes Niob-Bor-Silicium wird bei 1600° C mit Hilfe röntgenographischer und mikroskopischer Methoden ermittelt. Die T 2-Phase sowie die ternäre D 8₈-Phase besitzen einen ausgedehnten homogenen Bereich. Während Silicium in T 2 durch Bor bis annähernd Nb₅SiB₂ substituiert wird, besteht beim D 8₈-Typ eine Gitterauffüllung gemäß Nb₅Si₃B. Oxydationsversuche im Bereich von 400 bis 1200° C zeigen vor allem die Selektivität, indem Nb–Mk bzw. die Nb-Boride bevorzugt in Pentoxyd übergehen. Silicium übt einen stabilisierenden Einfluß auch auf das Bestehen von -Nb₂O₅ aus. -Nb₂O₅ tritt als Mischphase mit Anionendefekt auf, wodurch die sogenannte scharfe und diffuse Form erklärt wird. Die Umwandlungstemperatur - wird teilweise erheblich oberhalb der vonGoldschmidt angegebenen beobachtet. Die -Form wird als M-Modifikation nachBrauer identifiziert und relativ häufig nachgewiesen. Die -Form erweist sich alsBrauersche H-Modifikation und entsteht offensichtlich stufenweise (fast kontinuierlich) aus -Nb-Oxyd. Auf die Anionendefekt-Bildung wird nachdrücklich hingewiesen.Mit 3 Abbildungen     

Intercalation of Dyes Containing SO3H Groups into Zn–Al Layered Double Hydroxide

The intercalates of Naphthol Yellow S, Tropaeolin 000, and Tropaeolin 00 were prepared by heating [Zn_0.67Al_0.33(OH)₂](CO₃)_0.165 · 0.5H₂O with acidic forms of the dye solutions in an open reaction vessel. The intercalates were characterized by chemical and thermal analysis, X-ray powder diffraction and UV–VIS spectroscopy. A possible arrangement of the dye molecules in the intercalates was suggested on the basis of their chemical compositions and interlayer distances, by taking into account van der Waals dimensions of the guest molecules and by assuming that the structure of the host layers is not changed during the intercalation process.     

A theoretical study of the structure and bonding of UOX4 (X = F, Cl, Br, I) molecules: the importance of inverse trans influence.

During nitroxide-mediated polymerization (NMP) in the presence of a nitroxide R2(R1)NO*, the reversible formation of N-alkoxyamines [P-ON(R1)R2] reduces significantly the concentration of polymer radicals (P*) and their involvement in termination reactions. The control of the livingness and polydispersity of the resulting polymer depends strongly on the magnitude of the bond dissociation energy (BDE) of the C-ON(R1)R2 bond. In this study, theoretical BDEs of a large series of model N-alkoxyamines are calculated with the PM3 method. In order to provide a predictive tool, correlations between the calculated BDEs and the cleavage temperature (T(c)), and the dissociation rate constant (k(d)), of the N-alkoxyamines are established. The homolytic cleavage of the N-OC bond is also investigated at the B3P86/6-311++G(d,p)//B3LYP/6-31G(d), level. Furthermore, a natural bond orbital analysis is carried out for some N-alkoxyamines with a O-C-ON(R1)R2 fragment, and the strengthening of their C-ON(R1)R2 bond is interpreted in terms of stabilizing anomeric interactions.     

Boundary phase stability and critical phenomena in higher order solid solution systems II

The thermodynamic treatment of double-pseudobinary solutions of the type (A _xB_y) _{r o}(M _uN_v) _{s o} presented in a preceding publication was extended to include the conditions defining the critical points for the asymmetric case (r _os _o) and approximations for the spinodal and binodal surface near the critical solution point.Closed solutions for the coordinates of the critical points were obtained only for systems with ideal mixing behavior, and the isothermal binodal and spinodal near the critical solution point in such systems are adequately approximated by circles and ellipses, respectively. An axes ratio of is nearly independent of the relative sublattice abundance and the major effect of changes in the ratios _o/r _o is a rotation of the binodal by an angle tg .The principal features of nonideal regular systems for temperatures close to the critical solution point are described by expressions derived from small term expansions of the conditional equations, but generalizations are not possible to the same extent as for the case with ideal boundary systems. The results are discussed and the application of the equations demonstrated on model examples.Mit 6 Abbildungen     

Intercalation of 1,2-Alkanediols into α-Zirconium Hydrogenphosphate

Intercalation compounds of α-Zr(HPO₄)₂ · H₂O with 1,2-alkanediols (from C3 to C16) have been prepared by replacing 1-propanol in α-Zr(HPO₄)₂ · 2C₃H₇OH with the desired 1,2-alkanediols by a treatment in a microwave field. It was found that the intercalates contain 1.5 molecules of diol per formula unit. The diol molecules are placed between the host layers in a bimolecular way with their aliphatic chains tilted at an angle of 51°. The diol molecules are anchored in the interlayer space by H-bonds. A mixed intercalate, containing 1,2-butanediol and 1,2-decanediol in a roughly equimolar ratio, is formed when the α-Zr(HPO₄)₂ · 2C₃H₇OH intercalate, suspended in a mixture of 1,2-butanediol and 1,2-decanediol, is exposed to microwave radiation. No new phase containing both types of the guest molecules was observed when the 1-propanol intercalate, suspended in a mixture of 1-propanol and 1,2-octanediol, is exposed to microwave radiation.     

Mass spectrometric determination of glycosylation sites and oligosaccharide composition of insect-expressed mouse interleukin-3

The primary structure of Baculovirus-expressed mouse interleukin-3 produced in infected Bombyx mori larvae was characterized by liquid secondary ion mass spectrometry and 252Cf-plasma desorption mass spectrometry in combination with selected protein microchemical reactions. Interleukin-3 was found to consist of at least two glycoprotein species of ca. 17,000 dalton. Characterization of tryptic and S. aureus V8 protease peptides by Edman degradation combined with plasma desorption mass spectrometry showed that two N-glycosylation sites. Asn-16 and Asn-86, were present. N-Glycan residues were shown by liquid secondary ion mass spectrometry and high-performance liquid chromatography to consist of mannose, fucose, and glucosamine. The presence of galactosamine indicated that O-glycosylated residues were present, in addition to the N-glycosylated residues. Glucose was also present, which indicated incomplete processing of the insect-expressed N-linked oligosaccharides.