Kinematic analysis of Bricard’s mechanism

We show how the tools of computational algebra can be used to analyze the configuration space of multibody systems. One advantage of this approach is that the mobility can be computed without using the Jacobian of the system. As an example, we treat thoroughly the well-known Bricard’s mechanism, but the same methods can be applied to a wide class of rigid multibody systems. It turns out that the configuration space of Bricard’s system is a smooth closed curve, which can be explicitly parametrized. Our computations also yield a new formulation of constraints which is better than the original one from the point of view of numerical simulations.     

Fractal characteristics of critical and localized states in incommensurate quantum systems

Incommensurate quantum systems with two competing periodicities exhibit metallic (with Bloch-type extended wave functions), insulating (with exponentially localized wave functions) as well ascritical (with fractal wave functions) phases. An exact renormalization method, which takes into account the inherent incommensurability, is used to obtain the phase diagram of various quantum models for the two-dimensional electron gas and for quantum spin chains in a magnetic field. In this approach, the scaling properties of the fractal eigenstates are characterized by a fixed point or a strange invariant set of the renormalization flow. One of our novel results is the existence of self-similar fluctuations in the localized states once the exponentially decaying envelope is factorized out. In almost all cases under investigation here, the universality classes can be broadly classified as those of the nearest-neighbor square or triangular lattices.     

A special method of deformational correction in N.M.R. of molecules dissolved in liquid crystals

A simple method of deformational correction for the N.M.R. spectral parameters of molecules dissolved in liquid crystals is described. The method is applicable to the different isotopically substituted derivatives of the molecules belonging to the cubic point groups. Its validity is verified for the dipolar and quadrupolar couplings observed in the molecules CH₄, CD₄ and CH₃D dissolved in the liquid crystals Merck Phase IV, Merck ZLI 1167 and their mixtures.     

A comparative molecular field analysis of cytochrome P450 2A5 and 2A6 inhibitors

Structure-activity relationships of 23 P450 2A5 and 2A6 inhibitors were analysed using the CoMFA [1] and GOLPE/GRID with smart region definition (SRD) [2]. The predictive power of the resulting models was validated using five compounds not belonging to the model set. All models have high internal and external predictive power and resulting 3D-QSAR models are supporting each other. Both Sybyl and GOLPE highlight properties near lactone moiety to be important for 2A5 and 2A6 inhibition. Another important feature for pIC₅₀ was the size of the substituent in the 7-positon of coumarin. The models suggest that the 2A5 binding site is larger that that of 2A6 due to larger steric regions in the CoMFA coefficient maps and corresponding GOLPE maps. In addition, the maps reveal that 2A6 disfavours negative charge near the lactone moiety of coumarin.     

Copolymerisation properties of siloxy‐substituted bis(indenyl)zirconocene catalysts: modified rheological behaviour

The combination of the copolymerisation ability and vinyl end group selectivity of siloxy substitution of ethylene‐bridged bis(indenyl)zirconium dichlorides suggest these catalyst as potential ones for the production of polyethylene containing small amounts of long chain branching. The role of the polymerisation conditions with these highly active catalysts can clearly be seen. Furthermore low contents of multiple branches may occur, even though the probability of attaching several macromonomers into one chain is low. The effect on melt rheological behaviour depends on both the amount of long chain branching and the length of the branch. Moreover the position of the siloxy group is very important. Polymers synthesized with catalysts, where the siloxy group is in position 1, give peculiar rheological behaviour resembling cross‐linked networks although the polymers are completely soluble.     

An empirical constitutive model for complex glass-forming liquids using bitumen as a model material

While extensive research efforts have been devoted to understand the dynamics of chemically and structurally simple glass-forming liquids (SGFLs), the viscoelasticity of chemically and structurally complex glass-forming liquids (CGFLs) has received only little attention. This study explores the rheological properties of CGFLs in the vicinity of the glass transition. Bitumen is selected as the model material for CGFLs due to its extremely complex chemical composition and microstructure, fast physical aging and thermorheological simplicity, and abundant availability. A comprehensive rheological analysis reveals a significant broadening of the glass transition dynamics in bitumen as compared to SGFLs. In particular, the relaxation time spectrum of bitumen is characterized by a broad distribution of long relaxation modes. This observation leads to the development of a new constitutive equation, named the broadened power-law spectrum model. In this model, the wide distribution of long relaxation times is described by a power-law with positive exponent and a stretched exponential cut-off, with parameter β serving as a measure of the broadness of the distribution. This characteristic shape of the bitumen spectrum is attributed to the heterogeneous freezing of different molecular components of bitumen, i.e., to the coexistence of liquid and glassy micro-phases. Furthermore, as this type of heterogeneous glass transition behavior can be considered as a general feature of complex glass-forming systems, the broadened power-law spectrum model is expected to be valid for all types of CGFLs. Examples of the applicability of this model in various complex glass-forming systems are given.     

A special method of deformational correction in N.M.R. of molecules dissolved in liquid crystals

Abstract

A simple method of deformational correction for the N.M.R. spectral parameters of molecules dissolved in liquid crystals is described. The method is applicable to the different isotopically substituted derivatives of the molecules belonging to the cubic point groups. Its validity is verified for the dipolar and quadrupolar couplings observed in the molecules CH₄, CD₄ and CH₃D dissolved in the liquid crystals Merck Phase IV, Merck ZLI 1167 and their mixtures.     

Xenon porometry at room temperature

Xenon porometry is a method in which porous material is immersed in a medium and the properties of the material are studied by means of 129Xe nuclear magnetic resonance (NMR) of xenon gas dissolved in the medium. For instance, the chemical shift of a particular signal (referred to as signal D) arising from xenon inside small pockets formed in the pores during the freezing of the confined medium is highly sensitive to the pore size. In the present study, we show that when naphthalene is used as the medium the pore size distribution of the material can be determined by measuring a single one-dimensional spectrum near room temperature and converting the chemical shift scale of signal D to the pore radius scale by using an experimentally determined correlation. A model has been developed that explains the curious behavior of the chemical shift of signal D as a function of pore radius. The other signals of the spectra measured at different temperatures have also been identified, and the influence of xenon pressure on the spectra has been studied. For comparison, 129Xe NMR spectra of pure xenon gas adsorbed to porous materials have been measured and analyzed.     

Formation of Aromatic and Other Unsaturated End Groups in Carboxymethyl Cellulose During Hot Alkaline Treatment

Carboxymethyl cellulose (CMC, DS 0.58) was treated in solutions of sodium hydroxide (0.001–1 M) at 95 °C. The treated (1–12 h) CMC samples were purified by dialysis and analyzed by UV spectroscopy and by UV resonance Raman spectroscopy (UVRRS) with excitation at 244 nm. A UV absorption maximum at 265 nm and a UVRR signal at 1650 cm⁻¹ were indicative of formation of -conjugated aldehyde end groups in CMC through -elimination. Another strong UVRR band at 1610 cm⁻¹ gave evidence on conversion of some of the -conjugated aldehyde end groups to alkali stable aromatic structures.