Hydrogen-bonded supramolecular polymers as self-healing hydrogels: Effect of a bulky adamantyl substituent in the ureido-pyrimidinone monomer

In an attempt to generate supramolecular assemblies able to function as self-healing hydrogels, a novel ureido-pyrimidinone (UPy) monomer, 2-(N ′-methacryloyloxyethylureido)-6-(1-adamantyl)-4[1H]-pyrimidinone, was synthesized and then copolymerized with N,N-dimethylacrylamide at four different feed compositions, using a solution of lithium chloride in N,N-dimethylacetamide as the polymerization medium. The assembling process in the resulting copolymers is based on crosslinking through the reversible quadruple hydrogen bonding between side-chain UPy modules. The adamantyl substituent was introduced in order to create a “hydrophobic pocket” that may protect the hydrogen bonds against the disruptive effect of water molecules. Upon hydration to equilibrium, all copolymers generated typical hydrogels when their concentration in the hydrated system was at least 15%. The small-deformation rheometry showed that all hydrated copolymers were hydrogels that maintained a solid-like behavior, and that their extrusion through a syringe needle did not affect significantly this behavior, suggesting a self-healing capacity in these materials. An application as injectable substitutes for the eye's vitreous humor was proposed

Effect of water management practice on pesticide behavior in paddy water

The fate and transport of three herbicides commonly used in rice production in Japan were compared using two water management practices. The herbicides were simetryn, thiobencarb and mefenacet. The first management practice was an intermittent irrigation scheme using an automatic irrigation system (AI) with a high drainage gate and the second one was a continuous irrigation and overflow drainage scheme (CI) in experimental paddy fields. Dissipation of the herbicides appeared to follow first order kinetics with the half-lives (DT₅₀) of 1.6-3.4 days and the DT₉₀ (90% dissipation) of 7.4-9.8 days. The AI scheme had little drainage even during large rainfall events thus resulting in losses of less than 4% of each applied herbicide through runoff. Meanwhile the CI scheme resulted in losses of about 37%, 12% and 35% of the applied masses of simetryn, thiobencarb and mefenacet, respectively. The intermittent irrigation scheme using an automatic irrigation system with a high drainage gate saved irrigation water and prevented herbicide runoff whereas the continuous irrigation and overflow scheme resulted in significant losses of water as well as the herbicides. Maintaining the excess water storage is important for preventing paddy water runoff during significant rainfall events. The organic carbon partition coefficient K_oc seems to be a strong indicator of the aquatic fate of the herbicide as compared to the water solubility (S_W). However, further investigations are required to understand the relation between K_oc and the agricultural practices upon the pesticide fate and transport. An extension of the water holding period up to 10 days after herbicide application based on the DT₉₀ from the currently specified period of 3-4 days in Japan is recommended to be a good agricultural practice for controlling the herbicide runoff from paddy fields. Also, the best water management practice, which can be recommended for use during the water holding period, is the intermittent irrigation scheme using an automatic irrigation system with a high drainage gate. © 2006 Elsevier B.V. All rights reserved.

Effect of ion nitriding on the microstructure and properties of Maraging steel (250 Grade)

In the present investigation, ion nitriding of Maraging steel (250 grade) has been carried out at three different temperatures i.e., at 435 degrees C, 450 degrees C and 465 degrees C for 10 h duration in order to achieve good wear resistance along with high strength required for the slat track component of aircraft. The microstructure of the base material and the nitrided layer was examined by optical and scanning electron microscope, and various phases present were determined by X-ray diffraction. Various properties, such as, hardness, case depth, tensile, impact, fatigue properties and corrosion resistance were investigated for both un-nitrided and ion-nitrided materials. It is observed that the microstructure of the core material remains unaltered and Fe4N is formed in the hardened surface layer after ion nitriding at all the three temperatures employed. Surface hardness increases substantially after ion nitriding. Surface hardness remains almost the same but case depth increases with the increase in ion nitriding temperature due to greater diffusivity at higher temperatures. Tensile strength, fatigue strength and corrosion resistance are improved but ductility and energy absorbed in impact test decrease on ion nitriding. These results are explained on the basis of microstructural observations. The properties obtained after ion nitriding at 450 degrees C for 10 h are found to be optimum when compared to the other two ion nitriding temperatures.

Dynamics of a dilute sheared inelastic fluid. II. The effect of correlations

The effect of correlations on the viscosity of a dilute sheared inelastic fluid is analyzed using the ring-kinetic equation for the two-particle correlation function. The leading-order contribution to the stress in an expansion in epsilon=(1-e)(1/2) is calculated, and it is shown that the leading-order viscosity is identical to that obtained from the Green-Kubo formula, provided the stress autocorrelation function in a sheared steady state is used in the Green-Kubo formula. A systemmatic extension of this to higher orders is also formulated, and the higher-order contributions to the stress from the ring-kinetic equation are determined in terms of the terms in the Chapman-Enskog solution for the Boltzmann equation. The series is resummed analytically to obtain a renormalized stress equation. The most dominant contributions to the two-particle correlation function are products of the eigenvectors of the conserved hydrodynamic modes of the two correlated particles. In Part I, it was shown that the long-time tails of the velocity autocorrelation function are not present in a sheared fluid. Using those results, we show that correlations do not cause a divergence in the transport coefficients; the viscosity is not divergent in two dimensions, and the Burnett coefficients are not divergent in three dimensions. The equations for three-particle and higher correlations are analyzed diagrammatically. It is found that the contributions due to the three-particle and higher correlation functions to the renormalized viscosity are smaller than those due to the two-particle distribution function in the limit epsilon -> 0. This implies that the most dominant correlation effects are due to the two-particle correlations.

Difference spectroscopic studies on binding of Cibacron blue F3GA to ribosome inactivating proteins: effect of beta-mercaptoethanol on the interaction with ricin

The interaction of Cibacron blue F3GA with ribosome inactivating proteins, ricin, ricin A-chain and momordin has been investigated using difference absorption spectroscopy. Ricin was found to bind the dye with a 20- and 2-fold lower affinity than ricin A-chain and momordin, respectively. A time dependent increase in the amplitude of Cibacron blue difference spectrum in the presence of ricin was observed on addition of beta-mercaptoethanol. Analysis of the kinetic profile of this increase showed a biphasic phenomenon and the observed rates were found to be independent of the concentration of beta-mercaptoethanol. Kinetics of reduction of the intersubunit disulphide bond in ricin by beta-mercaptoethanol showed that reduction pet se is a second order reaction. Therefore, the observed changes in the difference spectra of Cibacron blue probably indicate a slow change in the conformation of ricin, triggered by reduction of the intersubunit disulphide bond.

Effect of Prior Ultraviolet Irradiation on Thermal Decomposition and Ignition of Coal

Prior ultraviolet irradiation of coal results in catalysing the subsequent thermal decomposition and ignition of coal. Mechanically, it is shown that ultraviolet radiation brings about the catalysis by acting on the inorganic components of coal.

Zeeman effect of chlorine nuclear quadrupole resonance and hydrogen bonding in 2,6-, 2,5- and 3,5-dichlorophenols

The Zeeman effect of chlorine nuclear quadrupole resonance in polycrystalline samples of 2,6-, 2,5 and 3,5-dichlorophenol has been investigated at room temperature in order to study the effect of hydrogen bonding on the electric field gradient asymmetry parameter n. While the two n.q.r. lines in 3,5-dichlorophenol gave an asymmetry parameter of 10%, those in 2,6- and 2,5-dichlorophenol gave different values of n for the two chlorines. The chlorine atom which is ortho to the OH group and involved in hydrogen bonding (i.e., corresponding to the low frequency line) gave an asymmetry parameter of 0.21 in 2,6-dichlorophenol and 0.17 in 2,5-dichlorophenol while the other chlorine (i.e., corresponding to the high frequency line) gave a lower value of 0.12 in 2,6-dichlorophenol and 0.11 in 2,5-dichlorophenol. These values of n are discussed in terms of hydrogen bonding and bond parameters.

Effect of a magnetic field on the flow and blood oxygenation in channels of variable cross-section

The effect of a magnetic field on the flow and oxygenation of an incompressible Newtonian conducting fluid in channels with irregular boundaries has been investigated. The geometric parameter δ, which is a ratio of the mean half width of the channel d to the characteristic length λ along the channel over which the significant changes in the flow quantities occur, has been used for perturbing the governing equations. Closed form solutions of the various order equations are presented for the stream function. The equations for oxygen partial pressure remain nonlinear even after perturbation, therefore a numerical solution is presented. The expressions for shear stress at a wall and pressure distributions are derived. Here the separation in the flow occurs at a higher Reynolds number than the corresponding non-magnetic case. It is found that the magnetic field has an effect on local oxygen concentration but has a little effect on the saturation length.

Compressible second-order boundary layers for three-dimensional stagnation point flows with mass transfer

All the second-order boundary-layer effects have been studied for the steady laminar compressible 3-dimensional stagnation-point flows with variable properties and mass transfer for both saddle and nodal point regions. The governing equations have been solved numerically using an implicit finite-difference scheme. Results for the heat transfer and skin friction have been obtained for several values of the mass-transfer rate, wall temperature, and also for several values of parameters characterizing the nature of stagnation point and variable gas properties. The second-order effects on the heat transfer and skin friction at the wall are found to be significant and at large injection rates, they dominate over the results of the first-order boundary layer, but the effect of large suction is just the opposite. In general, the second-order effects are more pronounced in the saddle-point region than in the nodal-point region. The overall heat-transfer rate for the 3-dimensional flows is found to be more than that of the 2-dimensional flows.

Effect of pressure on the resistivity of lead oxide-lead halide glasses

Resistivity behaviour of PbO---PbX2 (X=F,Cl) glasses has been investigated as a function of pressure at laboratory temperature. All PbO---PbX2 glasses undergo crystallization under pressure and the resistivities of crystallized samples are lower than the corresponding glasses. Transitions in PbO---PbF2 glasses exhibit a first order behaviour while transitions in PbO---PbCl2 glasses possess features of a continuous transition. The differences in the pressure behaviour of the two glass systems have been attributed to the differences in the ionic sizes of F− and Cl− ions and also to pressure induced modifications of Pb---O bonding.

Effect of phosphine dose on sorption in wheat

BACKGROUND: In spite of the extensive use of phosphine fumigation around the world to control insects in stored grain, and the knowledge that grain sorbs phosphine, the effect of concentration on sorption has not been quantified. A laboratory study was undertaken, therefore, to investigate the effect of phosphine dose on sorption in wheat. Wheat was added to glass flasks to achieve filling ratios of 0.25-0.95, and the flasks were sealed and injected with phosphine at 0.1-1.5 mg L-1 based on flask volume. Phosphine concentration was monitored for 8 days at 25°C and 55% RH. RESULTS: When sorption occurred, phosphine concentration declined with time and was approximately first order, i.e. the data fitted an exponential decay equation. Percentage sorption per day was directly proportional to filling ratio, and was negatively correlated with dose for any given filling ratio. Based on the results, a tenfold increase in dose would result in a halving of the sorption constant and the percentage daily loss. Wheat was less sorptive if it was fumigated for a second time. CONCLUSIONS: The results have implications for the use of phosphine for control of insects in stored wheat. This study shows that dose is a factor that must be considered when trying to understand the impact of sorption on phosphine concentration, and that there appears to be a limit to the capacity of wheat to sorb phosphine.

Pressure effect on the phase transition of trissarcosine calcium chloride

The dielectric measurement of ferroelectric trissarcosine calcium chloride (TSCC) was made under various pressures up to 6 kbar. A striking decrease in the peak value of the permittivity, epsilon r, at the transition temperature, Tc, was observed with increasing pressure. The value of Tc increases linearly with a pressure coefficient dTc/dp=11.1K kbar-1 at low pressures. This increase in Tc supports the suggestion that the ferroelectric transition is of the pure order-disorder type. It is suggested on the basis of the behaviour of epsilon r with pressure that the order of the ferroelectric transition changes from second to first order on application of pressure.

Defect Sensitization of Combustion and Thermal Decomposition of Ammonium Perchlorate: Effect of Pelletizing Pressure and Dwell Time

A systematic study was undertaken on the combustion and thermal decomposition of pelletized Ammonium Perchlorate (AP) to investigate the effects of pelletizing pressure and dwell time. At constant pressure, increasing the dwell time results in an increase in the burning rate up to a maximum and thereafter decreases it. The dwell time required for the pellets to have maximum burning rate is a function of pressure. The maximum burning rate is the same for all the pressures used and is also unaffected by increasing, to the range 90-250 μ, the particle size of AP used. In order to explain the occurrence of a maximum in burning rate, pellets were examined for their thermal sensitivities, physical nature and the changes occurring during pelletization with dwell time and pressure. The variations are argued in terms of increasing density, formation of defects such as dislocations leading to an increase in the number of reactive sites, followed by their partial annihilation at longer dwell times due to flow of material during pelletization.

Unsteady laminar compressible stagnation-point boundary-layer flow over a three-dimensional body: Higher order effects

The unsteady laminar compressible three-dimensional stagnation-point boundary-layer flow with variable properties has been studied when the velocity of the incident stream, mass transfer and wall temperature vary arbitrarily with time. The second-order unsteady boundary-layer equations for all the effects have been derived by using the method of matched asymptotic expansions. Both nodal and saddle point flows as well as cold and hot wall cases have been considered. The partial differential equations governing the flow have been solved numerically using an implicit finite-difference scheme. Computations have been carried out for an accelerating stream, a decelerating stream and a fluctuating stream. The results indicate that the unsteady free stream velocity distributions, the nature of the stagnation point, the mass transfer, the wall temperature and the variation of the density-viscosity product across the boundary significantly affect the skin friction and heat transfer. The variation of the wall temperature with time strongly affects the heat transfer whereas its effect is comparatively less on skin friction. Suction increases the skin friction and heat transfer but injection does the opposite. The skin friction in the x direction due to the combined effects of first- and second-order boundary layers is less than the skin-friction in the x direction due to the first-order boundary layers for all the parameters. The overall skin friction in the z direction and heat transfer are more or less than the first-order boundary layers depending upon the values of the various parameters.

Establishment and management of salt-tolerant amenity grasses to reduce urban salinity effect

This project built upon the successful outcomes of a previous project (TU02005) by adding to the database of salt tolerance among warm season turfgrass cultivars, through further hydroponic screening trials. Hydroponic screening trials focussed on new cultivars or cultivars that were not possible to cover in the time available under TU02005, including: 11 new cultivars of Paspalum vaginatum; 13 cultivars of Cynodon dactylon; six cultivars of Stenotaphrum secundatum; one accession of Cynodon transvaalensis; 12 Cynodon dactylon x transvaalensis hybrids; two cultivars of Sporobolus virginicus; five cultivars of Zoysia japonica; one cultivar of Z. macrantha, one common form of Z. tenuifolia and one Z. japonica x tenuifolia hybrid. The relative salinity tolerance of different turfgrasses is quantified in terms of their growth response to increasing levels of salinity, often defined by the salt level that equates to a 50% reduction in shoot yield, or alternatively the threshold salinity. The most salt tolerant species in these trials were Sporobolus virginicus and Paspalum vaginatum, consistent with the findings from TU02005 (Loch, Poulter et al. 2006). Cynodon dactylon showed the largest range in threshold values with some cultivars highly sensitive to salt, while others were tolerant to levels approaching that of the more halophytic grasses. Coupled with the observational and anecdotal evidence of high drought tolerance, this species and other intermediately tolerant species provide options for site specific situations in which soil salinity is coupled with additional challenges such as shade and high traffic conditions. By recognising the fact that a salt tolerant grass is not the complete solution to salinity problems, this project has been able to further investigate sustainable long-term establishment and management practices that maximise the ability of the selected grass to survive and grow under a particular set of salinity and usage parameters. Salt-tolerant turf grasses with potential for special use situations were trialled under field conditions at three sites within the Gold Coast City Council, while three sites, established under TU02005 within the Redland City Council boundaries were monitored for continued grass survival. Several randomised block experiments within Gold Coast City were established to compare the health and longevity of seashore paspalum (Paspalum vaginatum), Manila grass (Zoysia matrella), as well as the more tolerant cultivars of other species like buffalo grass (Stenotaphrum secundatum) and green couch (Cynodon dactylon). Whilst scientific results were difficult to achieve in the field situation, where conditions cannot be controlled, these trials provided valuable observational evidence of the likely survival of these species. Alternatives to laying full sod such as sprigging were investigated, and were found to be more appropriate for areas of low traffic as the establishment time is greater. Trials under controlled and protected conditions successfully achieved a full cover of Paspalum vaginatum from sprigs in a 10 week time frame. Salt affected sites are often associated with poor soil structure. Part of the research investigated techniques for the alleviation of soil compaction frequently found on saline sites. Various methods of soil de-compaction were investigated on highly compacted heavy clay soil in Redlands City. It was found that the heavy duplex soil of marine clay sediments required the most aggressive of treatments in order to achieve limited short-term effects. Interestingly, a well constructed sports field showed a far greater and longer term response to de-compaction operations, highlighting the importance of appropriate construction in the successful establishment and management of turfgrasses on salt affected sites. Fertiliser trials in this project determined plant demand for nitrogen (N) to species level. This work produced data that can be used as a guide when fertilising, in order to produce optimal growth and quality in the major turf grass species used in public parkland. An experiment commenced during TU02005 and monitored further in this project, investigated six representative warm-season turfgrasses to determine the optimum maintenance requirements for fertiliser N in south-east Queensland. In doing so, we recognised that optimum level is also related to use and intensity of use, with high profile well-used parks requiring higher maintenance N than low profile parks where maintaining botanical composition at a lower level of turf quality might be acceptable. Kikuyu (Pennisetum clandestinum) seemed to require the greatest N input (300-400 kg N/ha/year), followed by the green couch (Cynodon dactylon) cultivars ‘Wintergreen’ and ‘FLoraTeX’ requiring approximately 300 kg N/ha/year for optimal condition and growth. ‘Sir Walter’ (Stenotaphrum secundatum) and ‘Sea Isle 1’ (Paspalum vaginatum) had a moderate requirement of approximately 200 kg/ha/year. ‘Aussiblue’ (Digitaria didactyla)maintained optimal growth and quality at 100-200 kg N/ha/year. A set of guidelines has been prepared to provide various options from the construction and establishment of new grounds, through to the remediation of existing parklands by supporting the growth of endemic grasses. They describe a best management process through which salt affected sites should be assessed, remediated and managed. These guidelines, or Best Management Practices, will be readily available to councils. Previously, some high salinity sites have been turfed several times over a number of years (and Council budgets) for a 100% failure record. By eliminating this budgetary waste through targeted workable solutions, local authorities will be more amenable to investing appropriate amounts into these areas. In some cases, this will lead to cost savings as well as resulting in better quality turf. In all cases, however, improved turf quality will be of benefit to ratepayers, directly through increased local use of open space in parks and sportsfields and indirectly by attracting tourists and other visitors to the region bringing associated economic benefits. At the same time, environmental degradation and erosion of soil in bare areas will be greatly reduced.