PHOTOSENSITIZATION BY DRUGS: NALIDIXIC AND OXOLINIC ACIDS

Abstract— The antibacterial drugs, nalidixic acid and oxolinic acid, have been tested as photosensitizers in aqueous solution using 365 nm UV light. Absorption and fluorescence spectra indicate that intramolecular hydrogen bonding stabilizes the unionized form of these compounds in the pH region2–4. The ability of the unionized species to sensitize photooxidation by the type II (singlet oxygen) mechanism was found to be lower than when these drugs were ionized. Comparison withquinoline–3-carboxylic acid and the methyl esters of nalidixic and oxolinic acids emphasised the significance of the hydrogen bonding in relation to the excited state properties. Unionized nalidixic acid undergoes photolysis more readily than the ionized form, apparently by a free radical mechanism, while oxolinic acid is more stable.     

A DUAL-BEAM SOURCE OF ACTINIC LIGHT FOR PHOTOSYNTHESIS RESEARCH

Abstract— A dual-beam source for providing illumination of white or nearly monochromatic light for photosynthesis studies is presented. The device provides programmed, repetitive sample illumination with variable intensity, pulse duration and sequence and a means of monitoring that program. It utilizes a lamp with an integral heat rejecting reflector, and a fiber optic bundle which efficiently transmits the light, diffusely and evenly illuminating the sample.     

Demixing of a binary mixture in slit-like pores at high temperatures

We investigate the fluid—fluid demixing transitions in the case of adsorption of so-called symmetric binary mixtures in slit-like pores at temperatures higher than the bulk gas—liquid critical temperature. The aim of the study is to determine how the demixing of such mixtures in the pores depends on the bulk phase composition and on the parameters characterizing the pore. The calculations have been carried out by means of a density functional theory. In the case of an equimolar bulk mixture, the demixing transition inside the pore occurs only when the adsorption potentials of both species are identical. The occurrence of this transition is manifested by a cusp in the adsorption isotherm. For nonequimolar bulk phase compositions, the transition can also take place if the adsorption energies of both components are different. However, the difference in the adsorption energies should be small enough, otherwise a continuous demixing takes place. For non-equimolar compositions two branches of the grand canonical potential intersect, whereas for equimolar bulk composition they meet tangentially. We have determined phase behaviour for several model systems.     

On the low temperature anomalies in the properties of the electrochemical interface. A non-local free-energy density functional approach

The restricted primitive model has proved to be a useful system to describe the behaviour of electrical double layers. In this model, ions are represented by charged hard spheres of equal diameter and the solvent is represented by a uniform dielectric constant. Classical Gouy-Chapman's theory, and its modification by Stern, always predicts a monotonically decreasing capacitance for this system when the fluid's temperature is increased. Similar results are given by the mean spherical approximation. These predictions are in qualitative agreement with experiment for dissolved electrolytes, but disagree with molten salt experiments where capacitance increases with temperature. Additionally, recent Monte Carlo (MC) simulations for this model show that at very low temperatures, the capacitance of the interface, near its point of zero charge, increases with increasing temperature for both diluted and highly concentrated salts. In this work we apply a particular model of a non-local free-energy density functional theory to study the capacitance of the electrical interface. In our calculations we considered symmetrical 1:1 systems for both diluted electrolytes and highly concentrated salts at very low electrode surface charge. Density functional theory agrees very well with MC results for capacitance at high temperature, but fails to predict a positive slope for this property at low temperatures. Comparison of theoretical density profiles with MC results allows the exploration of possible causes of failure.     

THE INSURANCE VALUE OF BIODIVERSITY IN THE PROVISION OF ECOSYSTEM SERVICES

ABSTRACT. Biodiversity provides insurance against the uncertain provision of ecosystem services which are being used by risk‐averse economic agents. I present a conceptual ecological‐economic model that combines (i) current results from ecology about the relationships between biodiversity, ecosystem functioning, and the provision of ecosystem services with (ii) economic methods to study decision‐making under uncertainty. In this framework I (1) determine the insurance value of biodiversity, (2) study the optimal allocation of funds in the trade‐off between investing into biodiversity protection and the purchase of financial insurance, and (3) analyze the effect of different institutional regimes in the market for financial insurance on biodiversity protection. I conclude that biodiversity acts as a form of natural insurance for risk‐averse ecosystem managers against the over‐ or under‐provision with ecosystem services. Therefore, biodiversity has an insurance value, which is a value component in addition to the usual value arguments, such as direct or indirect use or non‐use values. In this respect, biodiversity and financial insurance are substitutes. Hence, the availability, and exact institutional design, of financial insurance influence the level of biodiversity protection.     

Density profiles and solvation force for a liquid in a slit

Computer simulations and density functional theory results are reported for a Lennard-Jones liquid in a slit or pore formed by two parallel hard walls. Both density profiles and solvation forces are computed. Two classes of calculation are performed. In the first class, a high bulk density is selected and, starting from a high temperature, the temperature is reduced until the temperature corresponding to bulk liquid—vapour coexistence is reached. For small slit widths or exceedingly large widths, the density in the slit decreases continuously until the slit is virtually empty or ‘dry’. When the slit width is somewhat larger than a molecular diameter, but still finite, the density in the slit decreases continuously as the temperature is decreased until there is an abrupt change in the density in the slit. Below this temperature, the density is smaller. Further decreases in the temperature, result in a continuous decrease in the slit density until the slit is virtually empty. In the second class, the density and temperature for bulk coexistence are chosen and the bulk density is increased. At the temperature and bulk density for bulk coexistence, the slit is virtually empty and remains so for all widths that we consider. As the bulk density is increased at constant temperature, the slit remains empty as the width is increased until some specific width is reached and then starts to fill abruptly. The agreement of the density functional and simulation results is qualitative but good.     

Statistical mechanics of Cassie's law

The wetting of chemically heterogeneous surfaces is typically discussed in terms of Cassie's law (1948, Discuss. Faraday Soc., 3, 11), which defines the cosine of the contact angle in terms of an average over the different chemical regions, weighted by their relative surface coverage. This paper derives an exact formulation of Cassie's law, in the context of the wetting of chemically patterned substrates. Deviations from Cassie's law arise from quasi-two-dimensional fluid-mediated interactions, analogous to solvation forces.     

MULTISPECIES AND SINGLE‐SPECIES MODELS OF FISH POPULATION DYNAMICS: COMPARING PARAMETER ESTIMATES

Abstract Population features inferred from single‐species, age‐structured models are compared to those inferred from a multispecies, age‐structured model that includes predator‐prey interactions among three commercially harvested fish species—walleye pollock, Atka mackerel, and Pacific cod—on the Aleutian Shelf, Alaska. The multispecies framework treats the single‐species models and data as a special case of the multispecies model and data. The same data from fisheries and surveys are used to estimate model parameters for both single‐species and multispecies configurations of the model. Additionally, data from stomach samples and predator rations are used to estimate the parameters of the multispecies model. One form of the feeding functional response, predator pre‐emption, was selected using AIC from seven alternative models for how the predation rate changes with the densities of prey and possibly other predators. Differences in estimated population dynamics and productivity between the multispecies and single‐species models were observed. The multispecies model estimated lower mackerel population sizes from 1964–2003 than the single‐species model, while the spawning biomass of pollock was estimated to have declined more than three times faster since 1964 by the multispecies model. The variances around the estimates of spawning biomass were smaller for mackerel and larger for pollock in the multispecies model compared to the single‐species model.     

On interfacial free energy versus interfacial stress of fluids adsorbed on chemically patterned surfaces: lessons from the special case of striped substrates

The statistical mechanics of fluids adsorbed on chemically patterned surfaces is far from straightforward when attempting to develop virial theorems for the interfacial free energy. This is because in general one would have to devise new procedures to distinguish surface tension from surface stress, even for wall-fluid models where the substrate atoms are replaced by an effective external field. However, the distinction may be made explicit for the special case of striped walls. This paper makes use of striped wall-fluid models to discuss the significance of fluid interfacial stress to patterned inhomogeneous fluids. In particular, it considers the adsorption of hemicylindrical drops on an array of high energy stripes. For the planar stripe geometry it is also possible to make effective use of the pressure tensor formalism. Beyond the special case of striped patterns it is not possible to use standard procedures based on virial theorems to directly evaluate interfacial free energy. The lessons learnt from these exercises apply especially to computer simulation studies of patterned inhomogeneous fluids.