Synthesis, NMR studies and conformational analysis of oxazolidine derivatives of the beta-adrenoreceptor antagonists metoprolol, atenolol and timolol

Formaldehyde-derived oxazolidine derivatives 4-7 of the beta-adrenoreceptor antagonists metoprolol 1, atenolol 2 and timolol 3 have been synthesised. Conformational analysis of 1-3 and the oxazolidine derivatives 4-7 has been performed using H-1 NMR spectroscopy and computational methods. The H-1 NMR studies show that for the aryloxypropanolamine beta-adrenoreceptor antagonists there is a predominance of the conformer in which the amine group is approximately antiperiplanar or trans to the aryloxymethylene group. Both H-1 NMR data and theoretical studies indicate that the oxazolidine derivatives 4-7 and the aryloxypropanolamine beta-adrenoreceptor antagonists 1-3 adopt similar conformations around the beta-amino alcohol moiety. Thus, oxazolidine ring formation does not dramatically alter the preferred conformation adopted by the beta-amino alcohol moiety of 1-3. Oxazolidine derivatives of aryloxypropanolamine beta-adrenoreceptor antagonists may therefore be appropriate as prodrugs, or semi-rigid analogues, when greater lipophilicity is required for drug delivery.

Turbulence in Small Sub-Tropical Estuary with Semi-Diurnal Tides

In natural estuaries, contaminant transport is driven by the turbulent momentum mixing. The predictions of scalar dispersion can rarely be predicted accurately because of a lack of fundamental understanding of the turbulence structure in estuaries. Herein detailed turbulence field measurements were conducted at high frequency and continuously for up to 50 hours per investigation in a small subtropical estuary with semi-diurnal tides. Acoustic Doppler velocimetry was deemed the most appropriate measurement technique for such small estuarine systems with shallow water depths (less than 0.5 m at low tides), and a thorough post-processing technique was applied. The estuarine flow is always a fluctuating process. The bulk flow parameters fluctuated with periods comparable to tidal cycles and other large-scale processes. But turbulence properties depended upon the instantaneous local flow properties. They were little affected by the flow history, but their structure and temporal variability were influenced by a variety of mechanisms. This resulted in behaviour which deviated from that for equilibrium turbulent boundary layer induced by velocity shear only. A striking feature of the data sets is the large fluctuations in all turbulence characteristics during the tidal cycle. This feature was rarely documented, but an important difference between the data sets used in this study from earlier reported measurements is that the present data were collected continuously at high frequency during relatively long periods. The findings bring new lights in the fluctuating nature of momentum exchange coefficients and integral time and length scales. These turbulent properties should not be assumed constant.

'Tetol': a stereo-rigid four-strand motif for alkali and alkaline earth metal ion coordination

The tetraalcohol 2,3,5,6-endo,endo,endo,endo-tetrakis(hydroxymethyl]bicyclo[2.2.1]heptane (tetol, 1) has been prepared and crystallises readily as the lithium(I) complex [Li(1)(2)]Cl, forming an oligomeric multi-chain structure in which pairs of alcohols from two crystallographically independent tetol molecules bind lithium ions tetrahedrally. However, formation of monomeric structures in solution is inferred from electrospray mass spectroscopy, which has also shown evidence of exchange of lithium ion in the complexed species by added alkaline earth ions. (C) 2000 Elsevier Science S.A. All rights reserved.

Water wave-driven seepage in marine sediments

The action of water waves moving over a porous seabed drives a seepage flux into and out of the marine sediments. The volume of fluid exchange per wave cycle may affect the rate of contaminant transport in the sediments. In this paper, the dynamic response of the seabed to ocean waves is treated analytically on the basis of pore-elastic theory applied to a porous seabed. The seabed is modelled as a semi-infinite, isotropic, homogeneous material. Most previous investigations on the wave-seabed interaction problem have assumed quasi-static conditions within the seabed, although dynamic behaviour often occurs in natural environments. Furthermore, wave pressures used in the previous approaches were obtained from conventional ocean wave theories: which are based on the assumption of an impermeable rigid seabed. By introducing a complex wave number, we derive a new wave dispersion equation, which includes the seabed characteristics (such as soil permeability, shear modulus, etc.). Based on the new closed-form analytical solution, the relative differences of the wave-induced seabed response under dynamic and quasi-static conditions are examined. The effects of wave and soil parameters on the seepage flux per wave cycle are also discussed in detail. (C) 2000 Elsevier Science Ltd. All rights reserved.

Analytical solution for tidal propagation in a coupled semi-confined/phreatic coastal aquifer

An analytical solution is derived for tidal fluctuations in a coupled coastal aquifer system consisting of a semi-confined aquifer, a thin semi-permeable layer and a phreatic aquifer. Based on the solution, we study the interactions (via leakage) between the confined and unconfined aquifers in response to tides. The results show that, under certain conditions, leakage from the confined aquifer can affect considerably the tidal water table fluctuation in the phreatic aquifer and vice versa. Ignoring these effects could lead to errors in estimating aquifer properties based on tidal signals. (C) 2002 Elsevier Science Ltd. All rights reserved.

Scope for further analytical solutions for constant flux infiltration into a semi-infinite soil profile or redistribution in a finite soil profile

[1] We attempt to generate new solutions for the moisture content form of the one-dimensional Richards' [1931] equation using the Lisle [1992] equivalence mapping. This mapping is used as no more general set of transformations exists for mapping the one-dimensional Richards' equation into itself. Starting from a given solution, the mapping has the potential to generate an infinite number of new solutions for a series of nonlinear diffusivity and hydraulic conductivity functions. We first seek new analytical solutions satisfying Richards' equation subject to a constant flux surface boundary condition for a semi-infinite dry soil, starting with the Burgers model. The first iteration produces an existing solution, while subsequent iterations are shown to endlessly reproduce this same solution. Next, we briefly consider the problem of redistribution in a finite-length soil. In this case, Lisle's equivalence mapping is generalized to account for arbitrary initial conditions. As was the case for infiltration, however, it is found that new analytical solutions are not generated using the equivalence mapping, although existing solutions are recovered.

Continental extension: From core complexes to rigid block faulting

Extension of overthickened continental crust is commonly characterized by an early core complex stage of extension followed by a later stage of crustal-scale rigid block faulting. These two stages are clearly recognized during the extensional destruction of the Alpine orogen in northeast Corsica, where rigid block faulting overprinting core complex formation eventually led to crustal separation and the formation of a new oceanic backarc basin (the Ligurian Sea). Here we investigate the geodynamic evolution of continental extension by using a novel, fully coupled thermomechanical numerical model of the continental crust. We consider that the dynamic evolution is governed by fault weakening, which is generated by the evolution of the natural-state variables (i.e., pressure, deviatoric stress, temperature, and strain rate) and their associated energy fluxes. Our results show the appearance of a detachment layer that controls the initial separation of the brittle crust on characteristic listric faults, and a core complex formation that is exhuming strongly deformed rocks of the detachment zone and relatively undeformed crustal cores. This process is followed by a transitional period, characterized by an apparent tectonic quiescence, in which deformation is not localized and energy stored in the upper crust is transferred downward and causes self-organized mobilization of the lower crust. Eventually, the entire crust ruptures on major crosscutting faults, shifting the tectonic regime from core complex formation to wholesale rigid block faulting.

A semi-empirical approach to optimise the quantity of drying aids required to spray dry sugar-rich foods

A semi-empirical linear equation has been developed to optimise the amount of maltodextrin additive (DE 6) required to successfully spray dry a sugar-rich product on the basis of its composition. Based on spray drying experiments, drying index values for individual sugars (sucrose, glucose, frutose) and citric acid were determined, and us;ng these index values an equation for model mixtures of these components was established. This equation has been tested with two sugar-rich natural products, pineapple juice and honey. The relationship was found to be valid for these products.

Improving wheat simulation capabilities in Australia from a cropping systems perspective: water and nitrogen effects on spring wheat in a semi-arid environment

Systems approaches can help to evaluate and improve the agronomic and economic viability of nitrogen application in the frequently water-limited environments. This requires a sound understanding of crop physiological processes and well tested simulation models. Thus, this experiment on spring wheat aimed to better quantify water x nitrogen effects on wheat by deriving some key crop physiological parameters that have proven useful in simulating crop growth. For spring wheat grown in Northern Australia under four levels of nitrogen (0 to 360 kg N ha(-1)) and either entirely on stored soil moisture or under full irrigation, kernel yields ranged from 343 to 719 g m(-2). Yield increases were strongly associated with increases in kernel number (9150-19950 kernels m(-2)), indicating the sensitivity of this parameter to water and N availability. Total water extraction under a rain shelter was 240 mm with a maximum extraction depth of 1.5 m. A substantial amount of mineral nitrogen available deep in the profile (below 0.9 m) was taken up by the crop. This was the source of nitrogen uptake observed after anthesis. Under dry conditions this late uptake accounted for approximately 50% of total nitrogen uptake and resulted in high (>2%) kernel nitrogen percentages even when no nitrogen was applied,Anthesis LAI values under sub-optimal water supply were reduced by 63% and under sub-optimal nitrogen supply by 50%. Radiation use efficiency (RUE) based on total incident short-wave radiation was 1.34 g MJ(-1) and did not differ among treatments. The conservative nature of RUE was the result of the crop reducing leaf area rather than leaf nitrogen content (which would have affected photosynthetic activity) under these moderate levels of nitrogen limitation. The transpiration efficiency coefficient was also conservative and averaged 4.7 Pa in the dry treatments. Kernel nitrogen percentage varied from 2.08 to 2.42%. The study provides a data set and a basis to consider ways to improve simulation capabilities of water and nitrogen effects on spring wheat. (C) 1997 Elsevier Science B.V.