Segmented polyurethane nanocomposites: Impact of controlled particle size nanofillers on the morphological response to uniaxial deformation

A series of TPU nanocomposites were prepared by incorporating organically modified layered silicates with controlled particle size. To our knowledge, this is the first study into the effects of layered silicate diameter in polymer nanocomposites utilizing the same mineral for each size fraction. The tensile properties of these materials were found to be highly dependent upon the size of the layered silicates. A decrease in disk diameter was associated with a sharp upturn in the stress-strain curve and a pronounced increase in tensile strength. Results from SAXS/SANS experiments showed that the layered silicates did not affect the bulk TPU microphase structure and the morphological response of the host TPU to deformation or promote/hinder strain-induced soft segment crystallization. The improved tensile properties of the nanocomposites containing the smaller nanofillers resulted from the layered silicates aligning in the direction of strain and interacting with the TPU sequences via secondary bonding. This phenomenon contributes predominantly above 400% strain once the microdomain architecture has largely been disassembled. Large tactoids that are unable to align in the strain direction lead to concentrated tensile stresses between the polymer and filler, instead of desirable shear stresses, resulting in void formation and reduced tensile properties. In severe cases, such as that observed for the composite containing the largest silicate, these voids manifest visually as stress whitening.

Temperature dependence of the crystal structure and g-values of [(HC(Ph2PO)(3))(2)Cu] (ClO4)(2)center dot 2H(2)O: Influence of dynamic Jahn-Teller coupling and lattice strain interactions

The temperature dependence of the X-ray crystal structure and powder EPR spectrum of [(HC(Ph2PO)(3))(2)CU]-(ClO4)(2)center dot 2H(2)O is reported, and the structure at room temperature confirms that reported previously. Below similar to 100 K, the data imply a geometry with near elongated tetragonal symmetry for the [(HC(Ph2PO)(3))(2)Cu](2+) complex, but on warming the two higher Cu-O bond lengths and g-values progressively converge, and by 340 K the bond lengths correspond to a compressed tetragonal geometry. The data may be interpreted satisfactorily assuming an equilibrium among the energy levels of a Cu-O-6 polyhedron subjected to Jahn-Teller vibronic coupling and a lattice strain. However, agreement with the experiment is obtained only if the orthorhombic component of the lattice strain decreases to a negligible value as the temperature approaches 340 K.

Dynamic annealing in III-nitrides under ion bombardment

We study the evolution of structural defects in AlxGa1-xN films (with x=0.0-0.6) bombarded with kilo-electron-volt heavy ions at 77 and 300 K. We use a combination of Rutherford backscattering/channeling spectrometry and cross-sectional transmission electron microscopy. Results show that an increase in Al content not only strongly enhances dynamic annealing processes but can also change the main features of the amorphization behavior. In particular, the damage buildup behavior at 300 K is essentially similar for all the AlGaN films studied. Ion-beam-produced disorder at 300 K accumulates preferentially in the crystal bulk region up to a certain saturation level (similar to50%-60% relative disorder). Bombardment at 300 K above a critical fluence results in a rapid increase in damage from the saturation level up to complete disordering, with a buried amorphous layer nucleating in the crystal bulk. However, at 77 K, the saturation effect of lattice disorder in the bulk occurs only for xgreater than or similar to0.1. Based on the analysis of these results for AlGaN and previously reported data for InGaN, we discuss physical mechanisms of the susceptibility of group-III nitrides to ion-beam-induced disordering and to the crystalline-to-amorphous phase transition. (C) 2004 American Institute of Physics.

Gelatinisation of starch in mixtures of sugars. I. Dynamic rheological properties and behaviours of starch-honey systems

Dynamic rheological behaviour of starch-honey systems was studied using a strain-controlled rheometer. A dynamic temperature (30-130 degreesC) ramp test was used at 10 rad s(-1) frequency, 1% strain, 2 degreesC min(-1) ramp rate, 25 mm parallel plate, and 1.5 min gap, using Wheaten cornflour(TM) and five honeys to generate 25 formulations (0.34-0.80 g water/g dry starch). G', G, and eta* increased upon gelatinisation, and they reduced as the honey content was increased. For all the formulations, G' was higher than G, and tan 6 was generally less than 1.0. Key gelatinisation characterising temperatures (onset, peak and end) ranged from 96.0 to 122.3 degreesC, but did not vary much (CV < 5%) for each honey irrespective of the concentration. The influence of water, fructose and glucose, singly and in combination, on gelatinisation indices (temperature and rheological parameters) was investigated. An exponential equation was employed to describe the relationship, and relevant parameters were obtained. The consequences of the observations in the study are discussed particularly as they relate to extrusion of such systems, and possible interactions between fructose and glucose in the starch-honey systems. (C) 2003 Elsevier Ltd. All rights reserved.

Response of the salt-freshwater interface in a coastal aquifer to a wave-induced groundwater pulse: field observations and modelling

Field observations on an unconfined coastal aquifer showed that a groundwater pulse, generated by it moderate (significant wave height, H-sig similar to 4.5 m) wave/storm event, induced significant oscillations in the salt-freshwater interface of the order of several metres in the horizontal direction. A dynamic sharp-interface model is developed to quantify the mechanism of these interface oscillations. The model uses the 50% seawater salinity contour as the location of the equivalent sharp-interface. The model was calibrated against the observed groundwater table fluctuations. It predicted reasonably well the interface oscillations with a slight over-prediction of the oscillation magnitude and a steepening of the interface. The neglect of mixing in the salt-freshwater mixing zone by the sharp-interface model is suggested as a possible contributor to the discrepancies between the model predictions and observations. In contrast with the significant wave effects, there was no observable response of the interface to diurnal or semidiurnal tides. (C) 2004 Elsevier Ltd. All rights reserved.

Lectin-induced haemocyte inactivation in insects

Most multimeric lectins are adhesion molecules, promoting attachment and spreading on surface glycodeterminants. In addition, some lectins have counter-adhesion properties, detaching already spread cells which then acquire round or spindle-formed cell shapes. Since lectin-mediated adhesion and detachment is observed in haemocyte-like Drosophila cells, which have haemomucin as the major lectin-binding glycoprotein, the two opposite cell behaviours may be the result of lectin-mediated receptor rearrangements on the cell surface. To investigate oligomeric lectins as a possible extracellular driving force affecting cell shape changes, we examined lectin-mediated reactions in lepidopteran haemocytes after cytochalasin D-treatment and observed that while cell-spreading was dependent on F-actin, lectin-uptake was less dependent on F-actin. We propose a model of cell shape changes involving a dynamic balance between adhesion and uptake reactions. (C) 2004 Elsevier Ltd. All rights reserved.

The LFA-1-associated molecule PTA-1 (CD226) on T cells forms a dynamic molecular complex with protein 4.1G and human discs large

Clustering of the T cell integrin, LFA-1, at specialized regions of intercellular contact initiates integrin-mediated adhesion and downstream signaling, events that are necessary for a successful immunological response. But how clustering is achieved and sustained is not known. Here we establish that an LFA-1-associated molecule, PTA-1, is localized to membrane rafts and binds the carboxyl-terminal domain of isoforms of the actin-binding protein 4.1G. Protein 4.1 is known to associate with the membrane-associated guanylate kinase homologue, human discs large. We show that the carboxyl-terminal peptide of PTA-1 also can bind human discs large and that the presence or absence of this peptide greatly influences binding between PTA-1 and different isoforms of 4.1G. T cell stimulation with phorbol ester or PTA-1 cross-linking induces PTA-1 and 4.1G to associate tightly with the cytoskeleton, and the PTA-1 from such activated cells now can bind to the amino-terminal region of 4.1G. We propose that these dynamic associations provide the structural basis for a regulated molecular adhesive complex that serves to cluster and transport LFA-1 and associated molecules.

MMTV-trBrca 1 mice display strain-dependent abnormalities in vaginal development

The breast cancer susceptibility gene Brca1 encodes a large multi-functional protein which is implicated as a caretaker of the genome, through its role in regulation of DNA damage response pathways, including apoptosis. Here we show that in mice expressing a dominant-negative Brca1 transgene on a BALB/c background, vaginal entrance remodeling is inhibited, and that the incidence of this phenotype is increased on a p53 +/- genotype. Given that this developmental process is mediated primarily by apoptosis, we hypothesized that disruption of BRCA1 may confer a resistance to apoptosis in normal epithelial cells. Consistent with this, we show that expression of this transgene in vitro leads to resistance to ionizing radiation induced cell killing in mammary epithelial cells. This is the first time that BRCA1 has been implicated in an apoptosis-mediated normal developmental process.

Dynamic and steady-state rheology of Australian honeys at subzero temperatures

The rheology of 10 Australian honeys was investigated at temperatures -15C to 0C by a strain-controlled rheometer. The honeys exhibited Newtonian behavior irrespective of the temperature, and follow the Cox-Merz rule. G/G' and omega are quadratically related, and the crossover frequencies for liquid to solid transformation and relaxation times were obtained. The composition of the honeys correlates well (r(2) > 0.83) with the viscosity, and with 24 7 data sets (Australian and Greek honeys), the following equation was obtained: mu = 1.41 x 10(-17) exp [-1.20M + 0.01F - 0.0G + (18.6 X 10(3)/T)] The viscosity of the honeys showed a strong dependence on temperature, and four models were examined to describe this. The models gave good fits (r(2) > 0.95), but better fits were obtained for the WLF model using T-g of the honeys and mu(g) = 10(11) Pa.s. The WLF model with its universal values poorly predicted the viscosity, and the implications of the measured rheological behaviors of the honeys in their processing and handling are discussed.

Transmission dynamics of the Echinococcus granulosus sheep-dog strain (G1 genotype) in camels in Tunisia

Cystic echinococcosis, caused by Echinococcus grantilosus, is highly endemic in North Africa and the Middle East. This paper examines the abundance and prevalence of infection of E. granulosus in camels in Tunisia. No cysts were found in 103 camels from Kebili, whilst 19 of 188 camels from Benguerden (10.1%) were infected. Of the cysts found 95% were considered fertile with the presence of protoscolices and 80% of protoscolices were considered viable by their ability to exclude aqueous eosin. Molecular techniques were used on cyst material from camels and this demonstrated that the study animals were infected with the G1 sheep strain of E. granulosus. Observed data were fitted to a mathematical model by maximum likelihood techniques to define the parameters and their confidence limits and the negative binomial distribution was used to define the error variance in the observed data. The infection pressure to camels was somewhat lower in comparison to sheep reported in an earlier study. However, because camels are much longer-lived animals, the results of the model fit suggested that older camels have a relatively high prevalence rate, reaching a most likely value of 32% at age 15 years. This could represent an important source of transmission to dogs and hence indirectly to man of this zonotic strain. In common with similar studies on other species, there was no evidence of parasite-induced immunity in camels. (C) 2004 Elsevier B.V. All rights reserved.

Comparison of the pharmacokinetics of oxycodone and noroxycodone in male dark agouti and Sprague-Dawley rats: Influence of streptozotocin-induced diabetes

Purpose. The aims of this study are to evaluate whether cytochrome P450 (CYP)2D1/2D2-deficient dark agouti (DA) rats and/or CYP2D1/2D2-replete Sprague-Dawley (SD) rats are suitable preclinical models of the human, with respect to mirroring the very low plasma concentrations of metabolically derived oxymorphone seen in humans following oxycodone administration, and to examine the effects of streptozotocin-induced diabetes on the pharmacokinetics of oxycodone and its metabolites, noroxycodone and oxymorphone, in both rodent strains. Methods. High-performance liquid chromatography-electrospray ionization-tandem mass spectrometry was used to quantify the serum concentrations of oxycodone, noroxycodone, and oxymorphone following subcutaneous administration of bolus doses of oxycodone (2 mg/kg) to groups of nondiabetic and diabetic rats. Results. The mean (+/- SEM) areas under the serum concentration vs. time curves for oxycodone and noroxycodone were significantly higher in DA relative to SD rats (diabetic, p < 0.05; nondiabetic, p < 0.005). Serum concentrations of oxymorphone were very low (< 6.9 nM). Conclusions. Both DA and SD rats are suitable rodent models to study oxycodone's pharmacology, as their systemic exposure to metabolically derived oxymorphone (potent mu-opioid agonist) is very low, mirroring that seen in humans following oxycodone administration. Systemic exposure to oxycodone and noroxycodone was consistently higher for DA than for SD rats showing that strain differences predominated over diabetes status.

Isolates of Candida albicans that differ in virulence for mice elicit strain-specific antibody-mediated protective responses

Three distinct isolates of Candida albicans were used to establish systemic and oral infections in inbred mice that are genetically resistant or susceptible to tissue damage. Patterns of infection differed significantly between both yeasts and mouse strains. Systemic infection conferred significant protection against re-challenge with the homologous, but not the heterologous yeast; however, the protective effect was more evident in the tissue-susceptible CBA/CaH mice than in the resistant BALB/c strain. In contrast, oral infection induced protection against both homologous and heterologous oral challenge, although this was significant only in the CBA/CaH mice. CBA/CaH mice produced antibodies of both IgG1 and IgG2a subclasses, whereas BALB/c mice produced predominantly IgG1. Western blotting demonstrated considerable differences between epitopes recognised by serum antibodies from mice of both strains after immunisation with each of the three yeasts. Thus, different strains of yeast show considerable specificity in antibody responses elicited by either systemic or oral infection. (c) 2005 Elsevier SAS. All rights reserved.

Dynamic assessment of articulation during lingual fatigue in myasthenia gravis

The present study aimed to investigate how induced lingual fatigue affected lingual strength, articulatory kinematics, and perceptual speech features in CS, a 51-year-old female with active myasthenia gravis (MG), and three age and gender matched control participants, Lingual fatigue was elicited via a series of endurance tasks using a tongue pressure bulb. Following each endurance task, the participants performed a speech task containing the phonemes /k/, /t/, and /j/ that was recorded with an electromagnetic articulograph, followed by a lingual strength assessment using a tongue pressure bulb. Participants repeated this schedule over five phases and kinematic and strength changes during each phase were compared to baseline measurements. All of CSs significant kinematic changes occurred during the final fatigue phase compared to 27.3% of the control group's kinematic changes occurring during this phase, suggesting the kinematic changes associated with fatigue were not accelerated in CS. The endurance tasks also elicited different kinematic effects for CSs anterior and posterior tongue segments. While CS exhibited mostly similar kinematic and perceptual changes to the control group, some of CS's perceptual transcriptions for /k/ and kinematic changes were not replicated, indicating that some different perceptual and physiological consequences to CS's speech were elicited by the endurance tasks.

In vivo demonstration of load-induced fluid flow in the rat tibia and its potential implications for processes associated with functional adaptation

Load-induced extravascular fluid flow has been postulated to play a role in mechanotransduction of physiological loads at the cellular level. Furthermore, the displaced fluid serves as a carrier for metabolites, nutrients, mineral precursors and osteotropic agents important for cellular activity. We hypothesise that load-induced fluid flow enhances the transport of these key substances, thus helping to regulate cellular activity associated with processes of functional adaptation and remodelling. To test this hypothesis, molecular tracer methods developed previously by our group were applied in vivo to observe and quantify the effects of load-induced fluid flow under four-point-bending loads. Preterminal tracer transport studies were carried out on 24 skeletally mature Sprague Dawley rats. Mechanical loading enhanced the transport of both small- and larger-molecular-mass tracers within the bony tissue of the tibial mid-diaphysis. Mechanical loading showed a highly significant effect on the number of periosteocytic spaces exhibiting tracer within the cross section of each bone. For all loading rates studied, the concentration of Procion Red tracer was consistently higher in the tibia subjected to pure bending loads than in the unloaded, contralateral tibia, Furthermore, the enhancement of transport was highly site-specific. In bones subjected to pure bending loads, a greater number of periosteocytic spaces exhibited the presence of tracer in the tension band of the cross section than in the compression band; this may reflect the higher strains induced in the tension band compared with the compression band within the mid-diaphysis of the rat tibia. Regardless of loading mode, the mean difference between the loaded side and the unloaded contralateral control side decreased with increasing loading frequency. Whether this reflects the length of exposure to the tracer or specific frequency effects cannot be determined by this set of experiments. These in vivo experimental results corroborate those of previous ex vivo and in vitro studies, Strain-related differences in tracer distribution provide support for the hypothesis that load-induced fluid flow plays a regulatory role in processes associated with functional adaptation.