Free volume and water uptake in a copolymer hydrogel series

A copolymer of X-hydroxyethyl methacrylate (HEMA) with 2-ethoxy ethyl methacrylate (EEMA) was synthesized and the molecular mobility, free volume, and density properties examined as a function of composition. These properties were correlated with the equilibrium water uptake in order to determine which of the properties were most influential in causing high water sorption, as these materials are suitable candidates for hydrogel systems. It was found that the polar HEMA repeat unit results in a rigid, glassy sample at room temperature due to the high degree of hydrogen bonding between chains whereas high EEMA content leads to rubbery samples with subambient glass transition temperatures. The free volume properties on the molecular scale measured by positron annihilation Lifetime spectroscopy (PALS) showed that higher HEMA content led to smaller, fewer holes and a lower free volume fraction than EEMA. Therefore the high water uptake of HEEMA-containing copolymers is largely related to the high polarity of the HEMA unit compared to EEMA, despite the low content of free volume into which the water can initially diffuse. Trends in density with copolymer composition, as measured on a macroscopic level, differs to that seen by PALS and indicates that the two techniques are measuring different scales of packing. (C) 1998 John Wiley & Sons, Inc.

Rheological behaviour of the mushy zone and its effect on the formation of casting defects during solidification

A new conceptual framework has been developed which explains the formation of shear-related casting defects such as porosity, segregation and tears. The theory relates defect formation to the mechanical behaviour of the partially solidified microstructure when shear stresses are developed during the filling of a casting and by the subsequent feeding processes during solidification. Two transition points, the dendrite coherency point and the maximum packing solid fraction, divide the mushy zone into three regions of different mechanical and feeding behaviours. The response of the mush to shear is related to the presence of these zones during solidification of a casting. The resulting defects are rationalized by considering the governing local shear stress and shear rate, local strength and time available for fluid flow. The design of the casting, the casting process used and the alloy composition all influence the relative importance of shearing on defect formation. (C) 1998 Acta Metallurgica Inc. Published by Elsevier Science Ltd. All rights reserved.

Role of compaction versus aggregate disruption on slumping and shrinking of repacked hardsetting seedbeds

Slumping of hardsetting seedbeds upon wetting is likely to determine the shrinking and development of strength on drying. Different processes have been invoked, including aggregate disruption, material relocation, and compaction. To gain a better understanding of the role played by compaction compared with aggregate disruption in seedbed slumping and shrinking, mechanical analysis was combined with previous morphogenetical description. The global structural behavior of repacked seedbeds of a hardsetting sandy loam soil was studied after wetting and again after subsequent drying. Bulk density was measured in 5-mm-depth increments using gamma attenuation, and water content was determined at 10-mm-depth increments. Various wetting conditions were used to simulate a range of climatic and management conditions, including flood irrigation, furrow irrigation of a formed seedbed, drip irrigation, and rainfall. Aggregate coalescence under overburden pressure played the main role in slumping, even though microcracking enhanced coalescence. Most of the slumping occurred at calculated effective stress > 1.1 kPa. Intense aggregate breakdown at the top of seedbeds under fast wetting led to slight slumping because the resulting clogging of the initial interaggregate packing voids was balanced, in part, by the increase in microporosity resulting from aggregate disruption. However, aggregate coalescence induced by overburden pressure developing at the seedbed bottom often resulted in a strong decrease in total porosity. The effect of rainfall kinetic energy on crust bulk density was strong compared with the effect of fast wetting (bulk density increase of about 0.07 Mg m(-3) and 0.03 Mg m(-3), respectively) and could be ascribed to compaction rather than to aggregate breakdown. Shrinking on drying was related to the continuity of the microstructure resulting from wetting rather than to the intensity of slumping. Aggregate breakdown led to more shrinking than did aggregate coalescence.

Solid-State Experimental and Theoretical Investigation of the Ammonium Salt of Croconate Violet, a Pseudo-Oxocarbon Ion

The present work describes the crystal structure, vibrational spectra, and theoretical calculations of ammonium salts of 3,5-bis-(dicyanomethylene)cyclopentane-1,2,4-trionate, (NH(4))(2)(C(11)N(4)O(3)) [(NH(4))(2)CV], also known as ammonium croconate violet. This compound crystallizes in triclinic P (1) over bar and contains two water molecules per unit formula. The crystal packing is stabilized by hydrogen bonds involving water molecules and ammonium cations, giving rise to a 3D polymeric arrangement. In this structure, a pi-stacking interaction is not observed, as the smaller centroid-centroid distance is 4.35 angstrom. Ab initio electronic structure calculations under periodic boundary conditions were performed to predict vibrational and electronic properties. The vibrational analysis was used to assist the assignments of the Raman and infrared bands. The solid structure was optimized and characterized as a minimum in the potential-energy surface. The stabilizing intermolecular hydrogen bonds in the crystal Structure were characterized by difference charge-density analysis. The analysis of the density of states of (NH(4))(2)CV gives an energy gap of 1.4 eV with a significant contribution of carbon and nitrogen 2p states for valence and conduction bands.

Incorporation of antigenic GPI-proteins from Leishmania amazonensis to membrane mimetic systems: Influence of DPPC/cholesterol ratio

The reconstitution of membrane proteins into liposomes is a useful tool to prepare antigenic components that induce immunity. We have investigated the influence of the dipalmitoylphosphatidylcholine (DPPC)/cholesterol molar ratio on the incorporation of a GPI-protein from Leishmania amazonensis on liposomes and Langmuir monolayers. The latter system is a well behaved and practical model, for understanding the effect of variables such as surface composition and lipid packing on protein incorporation. We have found that the DPPC/cholesterol molar ratio significantly alters the incorporation of the GPI-protein. In the absence of cholesterol, reconstitution is more difficult and proteoliposomes cannot be prepared, which we correlated with disruption of the DPPC layer. Our results provide important information that Could be employed in the development of a vaccine system for this disease or be used to produce other GPI-systems for biotechnological application. (c) 2009 Elsevier Inc. All rights reserved.

Surface miscibility of EPC/DOTAP/DOPE in binary and ternary mixed monolayers

Surface pressure (pi)-molecular area (A) curves were used to characterize the packing of pseudo-ternary mixed Langmuir monolayers of egg phosphatidylcholine (EPC), 1,2-dioleoyl-3-trimethylammonium propane (DOTAP) and L-alpha-dioleoyl phosphatidylethanolamine (DOPE). This pseudo-ternary mixture EPC/DOPE/DOTAP has been successfully employed in liposome formulations designed for DNA non-viral vectors. Pseudo-binary mixtures were also studied as a control. Miscibility behavior was inferred from pi-A curves applying the additivity rule by calculating the excess free energy of mixture (Delta G(Exc)). The interaction between the lipids was also deduced from the surface compressional modulus (C(s)(-1)). The deviation from ideality shows dependence on the lipid polar head type and monolayer composition. For lower DOPE concentrations, the forces are predominantly attractive. However, if the monolayer is DOPE rich, the DOTAP presence disturbs the PE-PE intermolecular interaction and the net interaction is then repulsive. The ternary monolayer EPC/DOPE/DOTAP presented itself in two configurations, modulated by the DOPE content, in a similar behavior to the DOPE/DOTAP monolayers. These results contribute to the understanding of the lipid interactions and packing in self-assembled systems associated with the in vitro and in vivo stability of liposomes. (C) 2010 Elsevier B.V. All rights reserved.

Machining of micro aspherical mould inserts

This paper reports a parametric investigation and development of grinding technologies for micro aspherical mould inserts using parallel grinding method. The parametric investigation revealed that at nanometric scale the undeformed chip thickness has little influence on the surface finish of ground inserts. The grinding trace spacing has a slightly larger influence on the surface finish. A new technique was developed to true and dress the resin bonded micro wheels with mesh size of #3000, which produced a satisfactory wheel form accuracy and relatively high grain packing density. A form error compensation technique was also developed, with which mould inserts of submicron form accuracy were consistently produced. Using the developed technologies, micro aspherical inserts of diameters ranging from 200 mu m to 1000 mu m with surface finish of around 10 nm and form error of similar to 0.2-0.4 mu m were successfully fabricated. (c) 2005 Elsevier Inc. All rights reserved.

Axial Young's modulus prediction of single-walled carbon nanotube arrays with diameters from nanometer to meter scales

Based on a self-similar array model, we systematically investigated the axial Young's modulus (Y-axis) of single-walled carbon nanotube (SWNT) arrays with diameters from nanometer to meter scales by an analytical approach. The results show that the Y-axis of SWNT arrays decreases dramatically with the increases of their hierarchy number (s) and is not sensitive to the specific size and constitution when s is the same, and the specific Young's modulus Y-axis(s) is independent of the packing configuration of SWNTs. Our calculations also show that the Y-axis of SWNT arrays with diameters of several micrometers is close to that of commercial high performance carbon fibers (CFs), but the Y-axis(s) of SWNT arrays is much better than that of high performance CFs. (C) 2005 American Institute of Physics.

The synergy between structural stability and DNA-binding controls the antibody production in EPC/DOTAP/DOPE liposomes and DOTAP/DOPE lipoplexes

We present a comparative study of the physico-chemical properties, in vitro cytotoxicity and in vivo antibody production of surface-complexed DNA in EPC/DOTAP/DOPE (50/25/25% molar) liposomes and DOTAP/DOPE (50/50% molar) lipoplexes. The study aims to correlate the biological behavior and structural properties of the lipid carriers. We used DNA-hsp65, whose naked action as a gene vaccine against tuberculosis has already been demonstrated. Additionally, surface-complexed DNA-hsp65 in EPC/DOTAP/DOPE (50/25/25% molar) liposomes was effective as a single-dose tuberculosis vaccine. The results obtained showed that the EPC inclusion stabilized the DOTAP/DOPE structure, producing higher melting temperature and lower zeta potential despite a close mean hydrodynamic diameter. Resemblances in morphologies were identified in both structures, although a higher fraction of loaded DNA was not electrostatically bound in EPC/DOTAP/DOPE. EPC also induced a striking reduction in cytotoxicity, similar to naked DNA-hsp65. The proper immune response lead to a polarized antibody production of the IgG2a isotype, even for the cytotoxic DOTAP/DOPE. However, the antibody production was detected at 15 and 30 days for DOTAP/DOPE and EPC/DOTAP/DOPE, respectively. Therefore, the in vivo antibody production neither correlates with the in vitro cytotoxicity, nor with the structural stability alone. The synergistic effect of the structural stability and DNA electrostatic binding upon the surface of structures account for the immunological effects. By adjusting the composition to generate proper packing and cationic lipid/DNA interaction, we allow for the optimization of liposome formulations for required immunization or gene therapy. In a specific manner, our results contribute to studies on the tuberculosis therapy and vaccination. (C) 2009 Elsevier B.V. All rights reserved.

The structures of Langmuir-Blodgett films of fatty acids and their salts

Recent advances in several experimental techniques have enabled detailed structural information to be obtained for floating (Langmuir) monolayers and Langmuir-Blodgett films. These techniques are described briefly and their application to the study of films of fatty acids and their salts is discussed. Floating monolayers on aqueous subphases have been shown to possess a complex polymorphism with phases whose structures may be compared to those of smectic mesophases. However, only those phases that exist at high surface pressures are normally used in Langmuir-Blodgett (LB) deposition. In single LB monolayers of fatty acids and fatty acid salts the acyl chains are in the all-cans conformation with their long axes normal to the substrate. The in-plane molecular packing is hexagonal with long-range bond orientational order and short-range positional order: known as the hexatic-B structure. This structure is found irrespective of the phase of the parent floating monolayer. The structures of multilayer LB films are similar to the structures of their bulk crystals, consisting of stacked bilayer lamellae. Each lamella is formed from two monolayers of fatty acid molecules or ions arranged head to head and held together by hydrogen bonding between pairs of acids or ionic bonding through the divalent cations. With acids the acyl chains are tilted with respect to the substrate normal and have a monoclinic structure, whereas the salts with divalent cations may have the chains normal to the substrate or tilted. The in-plane structures are usually centred rectangular with the chains in the trans conformation and packed in a herringbone pattern, Multilayer films of the acids show only a single-step order-disorder transition at the malting point, This temperature tends to rise as the number of layers increases. Complex changes occur when multilayer films of the salts are heated. Disorder of the chains begins at low temperatures but the arrangement of the head groups does not alter until the melting temperature is reached, Slow heating to a temperature just below the melting temperature gives, with some salts, a radical change in phase. The lamellar structure disappears and a new phase consisting of cylindrical rods lying parallel to the substrate surface and stacked in a hexagonal pattern is formed, In each rod the cations are aligned along the central axis surrounded by the disordered acyl chains. (C) 2001 Elsevier Science B,V. All rights reserved.

Structural effects of lipophilic methotrexate conjugates on model phospholipid biomembranes

Lipophilic conjugates of the antitumor drug methotrexate (MTX) with lipoamino acids (LAAs) have been previously described as a tool to enhance MTX passive entrance into cells, overcoming a form of transport resistance which makes tumour cells insensitive to the antimetabolite. A knowledge of the mechanisms of interaction of such lipophilic derivatives with cell membranes could be useful for planning further lipophilic MTX derivatives with an optimal antitumour activity. To this aim, a calorimetric study was undertaken using a biomembrane model made from synthetic 1,2-dipalmitoyl-glycero-3-phosphocholine (DPPC) multilamellar liposomes. The effects of MTX and conjugates on the phase transition of liposomes were investigated using differential scanning calorimetry. The interaction of pure MTX with the liposomes was limited to the outer part of the phospholipid bilayers, due to the polar nature of the drug. Conversely, its lipophilic conjugates showed a hydrophobic kind of interaction, perturbing the packing order of DPPC bilayers. In particular, a reduction of the enthalpy of transition from the gel to the liquid crystal phase of DPPC membranes was observed. Such an effect was related to the structure and mole fraction of the conjugates in the liposomes. The antitumour activity of MTX conjugates was evaluated against cultures of a CCRF-CEM human leukemic T-cell line and a related MTX resistant sub-line. The in vitro cell growth inhibitory activity was higher for bis(tetradecyl) conjugates than for both the other shorter- and longer-chain derivatives. The biological effectiveness of the various MTX derivatives correlated very well with the thermotropic effects observed on the phase transition of DPPC biomembranes. (C), 2001 Elsevier Science B.V All rights reserved.

Influence of fungal pathogens and environmental conditions on disease severity, flower fall and desiccation of harvested Geraldton waxflower - 2. Studies with commercial packages

Relationships were examined between environmental conditions mediated by packaging and handling and the deterioration of harvested Geraldton waxflower cv. 'Fortune Cookie'. Disease severity plus flower and leaf drop caused by inoculation with Botrytis cinerea were reduced by lowering handling temperatures to 0, 5 or 5/20 degreesC alternated daily, versus 20 degreesC. They were also reduced by inhibition of ethylene action with a silver thiosulfate pulse pretreatment. Additionally, treatments that enhanced water loss, such as packing dry, keeping forced air-cooling holes open and strategic placement of extra ventilation holes may also reduce disease severity and flower plus leaf fall. Inclusion of KMnO4-based Bloomfresh ethylene scrubbing sachets in packages did not reduce disease severity or lessen flower plus leaf fall. Thus, deterioration of waxflower packaged in commercial cartons can be minimised by keeping temperatures low, packing plant material dry, use of cartons with strategically placed ventilation holes and/or pretreatment with silver thiosulfate.

Experimental investigation of liquid flow shift due to gas cross flow in non-wetted packed beds

An experimental study has been carried out for the gas-liquid two-phase flow in a packed bed simulating conditions of the gas and liquid flows in the lower part of blast furnace. The localised liquid flow phenomenon in presence of gas cross flow, which usually occurs around the cohesive zone and raceway in blast furnace, was investigated in detail. Such liquid flow is characterised in terms of liquid shift distance or liquid shift angle that can effectively be measured by the experiments involved in the current study. It is found that liquid shift angle does not significantly increase or decrease with different packing depth. This finding supports the hypothesis of the force balance model where a vectorial relationship among acting forces, i.e. gas drag force, gravitational force and solid-liquid friction force, and liquid shift angle does exist. Liquid shift angle is inversely proportional to particle size and liquid density, and proportional to square of gas superficial velocity, but is almost independent on liquid flowrate and liquid viscosity. The gas-liquid drag coefficient, an important aspect for quantifying the interaction between gas and liquid flows, was conceptually modified based on the discrete feature of liquid flow through a packed bed and evaluated by the combined theoretical and experimental investigation. Experimental measurements suggest that the gas-liquid drag coefficient is approximately a constant (C-DG(')=5.4+/-1.0) and is independent on liquid properties, gas velocity and packing structure. The result shows a good agreement with previous experimental data and prediction of the existing liquid flow model.

The microbiological quality of beef tripe using different processing techniques

The microbiological quality of routinely processed tripe and rumen pillars were compared with those derived after emptying the rumen (paunch) without using water (dry dumping) and after deliberately bursting the paunches before processing. Prior to packing the mean:log(10) aerobic plate counts (APC) for the routinely processed tripe and rumen pillars were 3.55+/-1.08 and 3.28+/-0.87/g respectively. The corresponding mean log(10) total coliform counts (TCC) were 1.27+/-1.28 and 2.08+/-0.87. The mean log(10) APC counts on tripe and rumen pillars after dry-dumping were 3.06+/-0.60 and 3.90+/-0.75/g, respectively. The corresponding mean log(10) TCC were 1.03+/-0.60/g and 2.75+/-1.14/g respectively. After deliberately bursting the paunches, before processing, the mean log(10) APC counts on tripe and rumen pillars were 3.55+/-0.83/g and 3.50+/-0.59/g and the mean log(10) TCC were 1.54+/-0.95/g and 2.66+/-0.82/g respectively. In all cases the prevalence of Salmonella and Campylobacter spp. was less than 3%. The results indicate that both tripe and rumen pillars can be produced after dry dumping without compromising the quality of tripe and rumen pillars. Similarly, incidentally burst paunches that become contaminated with ingesta on the serosal surface can be processed without compromising product quality. Crown Copyright (C) 2002 Published by Elsevier Science Ltd. All rights reserved.

Unsaturated liquid percolation flow through nonwetted packed beds

The unsaturated flow of liquid through packed beds of large particles was studied using six different liquids, all with contact angles greater than 90degrees on the bed packing (wax spheres of 9, 15 and 19.4 mm diameter). The liquid flow was discrete in nature, as drops for low flow rates and rivulets for high flow rates. For unsaturated liquid flows, the actual percolation velocity, not superficial velocity, should be used to characterize the flow. The percolation velocity did not vary with packed-bed depth, but was a strong function of liquid flow rate, liquid and particle properties. Effects of liquid and particle properties (but not flow rate) are well captured by a simple correlation between the liquid-particle friction factor and Reynolds number based on actual percolation velocities. Liquid dispersion, characterized by the maximum dispersion angle, varies significantly with liquid and particle properties. The tentative correlation suggested here needs further validation for a wider range of conditions.