Structural changes in discotic samples during transition from crystal to discotic mesophase as revealed by electron microscopy and diffraction

Classical methods of structural analysis cannot be applied to liquid crystals because higher order reflections disappear during the transition from crystal to liquid crystal due to the reduction in long range orientational and translational correlations. However, in order to relate physical properties to the molecular architecture, it is essential to have information about molecular positions and orientations in the crystalline state as well as in the liquid crystalline state. In this work, the transition from crystalline to liquid crystalline phase is carefully monitored and the relationship between the original lattice and the new molecular positions found using electron diffraction. In addition to this, a new high resolution electron-microscopic technique is described in which the positions of molecules in the crystalline and the quenched discotic phase are directly imaged and the defects observed in the crystalline and LC phase compared and quantitatively analysed.     

Dibutyltin-3-hydroxyflavone titrates a dissociable component (cofactor) of mitochondrial ATP synthase: An energy-transfer component linked to the ubiquinone pool

Dibutyltin-3-hydroxyflavone, Bu₂Sn(of), is a new fluorescence probe inhibitor of F₁F₀-ATPase and oxidative phosphorylation which inhibits by titration of an unidentified component of F₀. Its site of action is closely related to that of the trialkyltins and of venturicidin. This F₀ component is part of a pool of this component which is present in the heart mitochondrial inner membrane at levels of 5–7 nmol (mg protein)^?1 [18 ± 3 Bu₂Sn(of) sites per mol F₁F₀-ATPase]. However, ATPase activity in submitochondrial particles is near maximally inhibited by titration of approx. three Bu₂Sn(of) sites per mol F₁F₀-ATPase. Over 60% (60–80%) of the Bu₂Sn(of) interaction sites can be lost during the purification of F₁F₀-ATPase from submitochondrial particles. The number of Bu₂Sn(of) interaction sites in various F₁F₀-ATPase preparations is variable. The high numbers of Bu₂Sn(of) sites per mol F₁F₀-ATPase for heart mitochondria (18–21) and submitochondrial particles (15–19.5) decline in ATP synthase (11–15) to the low values obtained in Complex V (7–10.5) and the minimal values observed in highly purified F₁F₀?ATPase (3.5–5.6), thus indicating a variable dissociable component or cofactor of ATP synthase. The Bu₂Sn(of) interaction site, a component of ATP synthase, is responsive to the redox status of the respiratory chain and the interaction with Bu₂Sn(of) is with the reduced form of this component. Fluorescence titration studies show that this component is in redox equilibrium with the ubiquinone pool of the respiratory chain. It is proposed that this redox component serves as an inhibitor titratable cofactor pool which cycles through an F₀ interaction site (or sites) via a system which serves as an energy-transfer link between the respiratory chain and ATP synthase.     

Trace determination of Tl, Cu, Pb, Cd, and Zn in specimens of the limnic environment using isotope dilution mass spectrometry with thermal ionization

Within the framework of the German Environmental Specimen Bank program, Tl, Cu, Pb, Cd and Zn were determined in homogenized materials from the limnic environment using Isotope Dilution Mass Spectrometry (IDMS) with thermal ionization. The analytical procedures which were developed for the trace metal analysis of bioindicator and sediment samples are described in detail. Results obtained in bream, mussels (Dreissena polymorpha) and sediments of Lake Constance/Estuary of Constance in the sampling years 1981, 1985, 1988, 1990, 1992 and 1993 are discussed and compared with those of bream from the lakeland district of Born-hoeved/Lake Belau and from the River Saar as well as from reference materials.     

The influence of the liquid crystalline core geometry on the mesogenicity of novel chiral 2-(4-substituted-phenoxy)propanonitriles

The synthesis and characterization of seven novel (R)-2-(4-substituted-phenoxy)propanonitriles are described. The propanonitriles were prepared to evaluate their potential use as thermochromics and ferroelectric dopants, as well as to determine their twist sense properties. The materials exhibit smectic and chiral nematic phases of high thermal stability; the mesogenic behaviour of the nitriles is directly related to the type of two-ring core unit employed. The effects of the different molecular geometries and polarizabilities of the liquid crystalline cores on mesophase stability are discussed, particularly in relation to other members of this series. The chiral nematic phase of the propanonitriles is assigned as having a left-handed twist sense from contact preparation studies, and this is in agreement with rules relating absolute configuration and molecular structure to helical twist sense.     

The Properties of Voronoi Tessellations for 2D Ising Fluid Near the Second-Order Magnetic Phase Transition

The topological and geometrical properties of Voronoi cells generated for 2D fluid of hard disks with Ising-like spins near the second-order phase transition from the paramagnetic to ferromagnetic phase are described for different disk densities. The comparison with Voronoi cells generated for the random hard disk system is given.     

Distribution of melamine in polyester–melamine surface coatings cured under nonisothermal conditions

The influence of experimental cure parameters on the diffusion of reactive species in polyester–melamine thermoset coatings during curing has been investigated with X‐ray photoelectron spectroscopy and attenuated total reflectance Fourier transform infrared. The diffusion of melamine plays a vital role in the curing process and, therefore, in the ultimate properties of coatings. At a low (<20%) hexamethoxymethylmelamine (HMMM) crosslinker concentration, the matrix composition is uniform, but at high HMMM concentrations, excess HMMM rapidly segregates to the air–coating interface. The rate of migration is governed by the difference in the surface free energies of polyester and HMMM and the concentration gradient of HMMM between the bulk and the surface. An increased rate of energy absorption also increases the rate of migration of HMMM to the surface. A physical model has been proposed to explain this surface segregation phenomenon in terms of cocondensation and self‐condensation reactions. It suggests that an appropriate amount of melamine can be segregated on the surface and allowed to self‐condense to form a desired thickness of a melamine topcoat through the control of the binder composition and cure conditions. This technique can be implemented to apply a melamine topcoat during cure. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 83–91, 2004