Crystal structures and thermal analyses of alkyl 2-deoxy-alpha-D-arabino-hexopyranosides

The crystal structures of alkyl 2-deoxy-alpha-D-arabino-hexopyranosides, with the alkyl chain lengths from C-8 to C-18, are established by the single crystal X-ray structural determination. The even-alkyl chain length derivatives crystallized orthorhombic, with space group P2(1)2(1)2(1), whereas the odd-alkyl chain length derivatives crystallized monoclinic, with space group P2(1). The sugar moieties retained a C-4(1) chair conformation and the conformation of the alkyl chains was all-trans. The molecules formed a bilayer structure, in which alkyl chains were interdigitated.The hydrogen bonds, originating from the sugar moieties, were observed in adjacent layers and also within the same layer, resulting in the formation of infinite chains. The alkyl chains arranged parallel to each other and formed planar structures. The thermal properties of the alkyl 2-deoxy glucosides were analyzed further. It was observed that none of the derivatives exhibited mesomorphism. This study establishes that the absence of the hydroxyl group at C-2 of the sugar moiety results in a non-mesogenic nature of the alkyl 2-deoxy-alpha-D-glycosides, as opposed to the profound mesogenic nature of the normal alkyl glycosides.

Improved procedures for static and dynamic analyses of wrinkled membranes

An analysis of large deformations of flexible membrane structures within the tension field theory is considered. A modification-of the finite element procedure by Roddeman et al. (Roddeman, D. G., Drukker J., Oomens, C. W J., Janssen, J. D., 1987, ASME J. Appl. Mech. 54, pp. 884-892) is proposed to study the wrinkling behavior of a membrane element. The state of stress in the element is determined through a modified deformation gradient corresponding to a fictive nonwrinkled surface. The new model uses a continuously modified deformation gradient to capture the location orientation of wrinkles more precisely. It is argued that the fictive nonwrinkled surface may be looked upon as an everywhere-taut surface in the limit as the minor (tensile) principal stresses over the wrinkled portions go to zero. Accordingly, the modified deformation gradient is thought of as the limit of a sequence of everywhere-differentiable tensors. Under dynamic excitations, the governing equations are weakly projected to arrive at a system of nonlinear ordinary differential equations that is solved using different integration schemes. It is concluded that, implicit integrators work much better than explicit ones in the present context.

Parametric finite element analyses of geocellsupported embankments

This paper presents the results from parametric finite element analyses of geocell-supported embankments constructed on weak foundation soils. A composite model is used to numerically simulate the improvement in the strength and stiffness of the soil as a result of geocell confinement. The shear strength of the geocell-encased soil is obtained as a function of the additional confining pressure due to the geocell encasement considering it as a thin cylinder subjected to internal pressure. The stiffness of the geocell-encased soil is obtained from the stiffness of the unreinforced soil and the tensile modulus of the geocell material using an empirical equation. The validity of the model is verified by simulating the laboratory experiments on model geocell-supported embankments. Parametric finite element analyses of the geocell-supported embankments are carried out by varying the dimensions of the geocell layer, the tensile strength of the material used for fabricating the geocell layer, the properties of the infill soil, and the depth of the foundation layer. Some important guidelines for selecting the geocell reinforcement to support embankments on weak foundation soils are established through these numerical studies.

Synthesis of neoglycopeptides and analyses of their biodistributionin vivo to identify tissue specific uptake and novel putative membrane lectins

Complex typeN-linked oligosaccharides derived from fetuin, fibrinogen and thyroglobulin were coupled to acetyltyrosine affording a series of neoglycopeptides with retention of terminal structures and the beta-anomeric configuration of their reducing endN-acetylglycosamine residue. The neoglycopeptides thus synthesized could be labelled to high specific activities with125I in the aromatic side chain of tyrosine. Analysis of the fate of these neoglycopeptides in conjunction with inhibition with asialofetuin and oligosaccharides of defined structure in micein vivo revealed the uptake of galactosylated biantennary compound by kidneys, in addition to the known itinerary of triantennary galactosylated complex oligosaccharide from fetuin to liver and the galactosylated biantennary chain with fucosylation in the core to bone marrows. On the other hand, the agalacto, aglucosamino biantennary chains with and without fucosylation in the core region are taken up by submaxillary glands while the conserved trimannosyl core with fucose is primarily concentrated in stomach tissue. These studies thus define new routes for the uptake of complexN-linked glycans and also subserve to identify lectins presumably involved in their recognition.

Selective Homonuclear Decoupling in H-1 NMR: Application to Visualization of Enantiomers in Chiral Aligning Medium and Simplified Analyses of Spectra in Isotropic Solutions

The proton NMR spectral complexity arising due to severe overlap of peaks hampers their analyses in diverse situations, even by the application of two-dimensional experiments. The selective or complete removal of the couplings and retention of only the chemical shift interactions in indirect dimension aids in the simplification of the spectrum to a large extent with little investment of the instrument time. The present study provides precise enantiodiscrimination employing more anisotropic NMR parameters in the chiral liquid crystalline medium and differentiates the overlapped peaks of many organic molecules and peptides dissolved in isotropic solvents.

A Comparative Study of Liapunov Stability Analyses of Flexible Damped Satellites

A literal Liapunov stability analysis of a spacecraft with flexible appendages often requires a division of the associated dynamic potential into as many dependent parts as the number of appendages. First part of this paper exposes the stringency in the stability criteria introduced by such a division and shows it to be removable by a “reunion policy.” The policy enjoins the analyst to piece together the sets of criteria for each part. Employing reunion the paper then compares four methods of the Liapunov stability analysis of hybrid dynamical systems illustrated by an inertially coupled, damped, gravity stabilized, elastic spacecraft with four gravity booms having tip masses and a damper rod, all skewed to the orbital plane. The four methods are the method of test density function, assumed modes, and two and one-integral coordinates. Superiority of one-integral coordinate approach is established here. The design plots demonstrate how elastic effects delimit the satellite boom length.

Effect of Neutralization of Endogenous Follicle Stimulating Hormone (FSH) or Luteinizing Hormone (LH) on Ovarian Lipids in the Hamster: A Histochemical and Biochemical Evaluation

The effect of neutralizing FSH or LH on ovarian lipids in the cycling hamster was studied. In the normal cycling hamster on the day of proestrus, histochemical examination revealed the presence of sudanophilic lipids in the granulosa cells of the follicles and in the interstitium. A clear reduction in the intensity of lipid staining was observed on proestrus in the ovary of hamsters treated with FSH antiserum on the previous proestrus. Similar treatment with antiserum to LH, on the other hand, caused an accumulation of lipids in these structures. Estimation of the free and esterified fractions of cholesterol and triglycerides in the nonluteal tissue of the ovary of hamsters on proestrus following treatment with FSH antiserum on the previous proestrus revealed a significant reduction in all 3 lipid components. Even a short term deprivation of FSH caused a similar reduction in these lipids in the ovary. In contrast, treatment with LH antiserum either on the previous proestrus or on the previous day (diestrus-2) resulted in an enhancement in esterified cholesterol and triglycerides, while it caused a reduction in the free cholesterol fraction of the ovary on proestrus.It is suggested that though treatment with antisera to either FSH or LH causes a disruption in follicular maturation, their effect on lipid metabolism is different. A positive role for FSH and LH in maintaining normal sterol and triglyceride levels in the nonluteal ovarian tissue of cycling hamster is indicated.

Comparative Analyses of Age- and Sex-Specific Patterns of Vocal Behaviour in Four Species of Old World Monkeys

Sound recordings and behavioural data were collected from four primate species of two genera (Macaca, Presbytis). Comparative analyses of structural and behavioural aspects of vocal communication revealed a high degree of intrageneric similarity but striking intergeneric differences. In the two macaque species (Macaca silenus, Macaca radiata), males and females shared the major part of the repertoire. In contrast, in the two langurs (Presbytis johnii, Presbytis entellus), many calls were exclusive to adult males. Striking differences between both species groups occurred with respect to age-specific patterns of vocal behaviour. The diversity of vocal behaviour was assessed from the number of different calls used and the proportion of each call in relation to total vocal output for a given age/sex class. In Macaca, diversity decreases with the age of the vocalizer, whereas in Presbytis the age of the vocalizer and the diversity of vocal behaviour are positively correlated. A comparison of the data of the two genera does not suggest any causal relationship between group composition (e.g. multi-male vs. one-male group) and communication system. Within each genus, interspecific differences in vocal behaviour can be explained by differences in social behaviour (e.g. group cohesion, intergroup relation, mating behaviour) and functional disparities. Possible factors responsible for the pronounced intergeneric differences in vocal behaviour between Macaca and Presbytis are discussed.

Preparation, characterization, spectral and thermal analyses of (N2H5)2MCl4·2H2O (M = Fe, Co, Ni and Cu); crystal structure of the iron complex

Hydrazinium metal chlorides, (N2H5)2MCl4·2H2O (where M = Fe, Co, Ni and Cu), have been prepared from the aqueous solutions of the respective metal chlorides and hydrazine hydrochloride (N2H4·HCl or N2H4·2HCl) and investigated by spectral and thermal analyses. The crystal structure of the iron complex has been determined by direct methods and refined by full-matrix least-squares to an R of 0.023 and Rw of 0.031 for 1495 independent reflections. The structure shows ferrous ion in an octahedral environment bonded by two hydrazinium cations, two chloride anions and two water molecules. In the complex cation [Fe(N2H5)2(H2O)2Cl2]2+, the coordinated groups are in trans positions.

Asymptotic and finite element analyses of mode III dynamic crack growth at a ductile-brittle interface

In this work, dynamic crack growth along a ductile-brittle interface under anti-plane strain conditions is studied. The ductile solid is taken to obey the J(2) flow theory of plasticity with linear isotropic strain hardening, while the substrate is assumed to exhibit linear elastic behavior. Firstly, the asymptotic near-tip stress and velocity fields are derived. These fields are assumed to be variable-separable with a power singularity in the radial coordinate centered at the crack tip. The effects of crack speed, strain hardening of the ductile phase and mismatch in elastic moduli of the two phases on the singularity exponent and the angular functions are studied. Secondly, full-field finite element analyses of the problem under small-scale yielding conditions are performed. The validity of the asymptotic fields and their range of dominance are determined by comparing them with the results of the full-field finite element analyses. Finally, theoretical predictions are made of the variations of the dynamic fracture toughness with crack velocity. The influence of the bi-material parameters on the above variation is investigated.

Synthesis, properties, and comparative analyses on the chain flexibility of an ultrastable vinyl polyperoxide

The most stable vinyl polyperoxide, namely, poly(indene peroxide) (PINDP), an alternating copolymer of indene and oxygen, was synthesized by the oxidative polymerization of indene. It was characterized by H-1-NMR and C-13-NMR, Fourier transform infrared, differential scanning calorimetry, direct pyrolysis mass spectrometry, and gas chromatography mass spectrometry studies. The overall activation energy for the degradation and the glass-transition temperature of PINDP were 47 kcal/mol and 327 K respectively, which were very high compared to those of other vinyl polyperoxides. (C) 2002 Wiley Periodicals, Inc.

Constitutive Response of Passivated Copper Films: Experiments and Analyses

The constitutive behavior of passivated copper films is studied. Stresses in copper films of thickness ranging from 1000 nm to 40 nm, passivated with silicon oxide on a quartz or silicon substrate, were measured using the curvature method. The thermal cycling spans a temperature range from - 196 to 600°C. It is seen that the strong relaxation at high temperatures normally found in unpassivated films is nonexistent for passivated films. The copper film did not show any rate-dependent effect over a range of heating/cooling rate from 5 to 25°C/min. Further analyses showed that significant strain hardening exists during the course of thermal loading. In particular, the measured stress- temperature response can only be fitted with a kinematic hardening model, if a simple constitutive law within the continuum plasticity framework is to be used. The analytic procedures for extracting the film properties are presented. Implications to stress modeling of copper interconnects in actual devices are discussed.

Oneand twodimensional single quantumand multiplequantumNMR methodologies: tools for chiral analyses

It is well known that enantiomers cannot be distinguished by NMR spectroscopy unless diastereomorphic interactions are imposed. Several chiral aligning media have therefore been reported for their visualization, although extensive studies are carried out using the liquid crystal made of polypeptide poly-γ-benzyl-L-glutamate (PBLG) in organic solvent. In PBLG medium the spin systems are weakly coupled and the first order analyses of the spectra are generally possible. But due to large number of pair wise interactions of nuclear spins resulting in many degenerate transitions the 1H NMR spectra are not only complex but also broad and featureless, in addition to an indistinguishable overlap of the spectra of enantiomers. This enormous loss of resolution severely hinders the analyses of proton spectra, even for spin systems with 5–6 interacting protons, thereby restricting itsroutine application. In this review we discuss our recently developed several one and multidimensional NMR experiments to circumvent these difficulties taking specific examples of the molecules containing a single chiral centre.