Electrolyte solutions at curved electrodes. I. Mesoscopic approach.

Within the Poisson-Boltzmann approach, electrolytes in contact with planar, spherical, and cylindrical electrodes are analyzed systematically. The dependences of their capacitance C on the surface charge density σ and the ionic strength I are examined as a function of the wall curvature. The surface charge density has a strong effect on the capacitance for small curvatures, whereas for large curvatures the behavior becomes independent of σ. An expansion for small curvatures gives rise to capacitance coefficients which depend only on a single parameter, allowing for a convenient analysis. The universal behavior at large curvatures can be captured by an analytic expression.

Electrolyte solutions at curved electrodes. II. Microscopic approach.

Density functional theory is used to describe electrolyte solutions in contact with electrodes of planar or spherical shape. For the electrolyte solutions, we consider the so-called civilized model, in which all species present are treated on equal footing. This allows us to discuss the features of the electric double layer in terms of the differential capacitance. The model provides insight into the microscopic structure of the electric double layer, which goes beyond the mesoscopic approach studied in Paper I. This enables us to judge the relevance of microscopic details, such as the radii of the particles forming the electrolyte solutions or the dipolar character of the solvent particles, and to compare the predictions of various models. Similar to Paper I, a general behavior is observed for small radii of the electrode in that in this limit the results become independent of the surface charge density and of the particle radii. However, for large electrode radii, non-trivial behaviors are observed. Especially the particle radii and the surface charge density strongly influence the capacitance. From the comparison with the Poisson-Boltzmann approach, it becomes apparent that the shape of the electrode determines whether the microscopic details of the full civilized model have to be taken into account or whether already simpler models yield acceptable predictions.

Large-scale phenotyping of transgenic tobacco plants (Nicotiana tabacum) to identify essential leaf functions.

Two of the major challenges in functional genomics are to identify genes that play a key role in biological processes, and to elucidate the biological role of the large numbers of genes whose function is poorly characterized or still completely unknown. In this study, a combination of large-scale expressed sequence tag sequencing, high-throughput gene silencing and visual phenotyping was used to identify genes in which partial inhibition of expression leads to marked phenotypic changes, mostly on leaves. Three normalized tobacco (Nicotiana tabacum) cDNA libraries were prepared directly in a binary vector using different tissues of tobacco as an RNA source, randomly sequenced and clustered. The Agrobacterium-tobacco leaf disc transformation system was used to generate sets of antisense or co-suppression transgenic tobacco plants for over 20 000 randomly chosen clones, each representing an independent cluster. After transfer to the glasshouse, transgenic plants were scored visually after 10-14 days for changes in growth, leaf form and chlorosis or necrosis. Putative hits were validated by repeating the transformation. This procedure is more stringent than the analysis of knockout mutants, because it requires that even a partial decrease in expression generates a phenotype. This procedure identified 88 validated gene/phenotype relations. These included several previously characterized gene/phenotype relationships, demonstrating the validity of the approach. For about one-third, a function could be inferred, but a loss-of-function phenotype had not been described previously. Strikingly, almost one-half of the validated genes were poorly annotated, or had no known function. For 77 of these tobacco sequences, a single or small number of potential orthologues were identified in Arabidopsis. The genes for which orthologues were identified in Arabidopsis included about one-half of the genes whose function was completely unknown. Comparison with published gene/phenotype relations for Arabidopsis knockout mutants revealed surprisingly little overlap with the present study. Our results indicate that partial gene silencing identifies novel gene/phenotype relationships, which are distinct from those uncovered by knockout screens. They also show that it is possible to perform these analyses in a crop species in which full genome sequence information is lacking, and subsequently to transfer the information to a reference species in which functional studies can be performed more effectively.

Target-based discovery of novel herbicides.

In the past 10 years, strategies for the first steps of herbicide discovery have switched from the testing of chemicals for efficacy on whole plants towards the use of in-vitro assays against molecular targets. Many different approaches have been developed to identify bona fide targets for in-vitro screening. Developments in functional genomics and in pharmaceutical research could aid the development of assay systems for the evaluation of chemicals for their suitability as lead structures in herbicide discovery.

Implications of interface conventions for morphometric thermodynamics.

Several model fluids in contact with planar, spherical, and cylindrical walls are investigated for small number densities within density functional theory. The dependence of the solid-fluid interfacial tension on the curvature of spherical and cylindrical walls is examined and compared with the corresponding expression derived within the framework of morphometric thermodynamics. Particular attention is paid to the implications of the choice of the interface location, which underlies the definition of the interfacial tension. We find that morphometric thermodynamics is never exact for the considered systems and that its quality as an approximation depends sensitively on the choice of the interface location.

Impedance spectroscopy of ions at liquid-liquid interfaces.

The possibility to extract properties of an interface between two immiscible liquids, e.g., electrolyte solutions or polyelectrolyte multilayers, by means of impedance spectroscopy is investigated theoretically within a dynamic density-functional theory which is equivalent to the Nernst-Planck-Poisson theory. An approach based on a two-step fitting procedure of an equivalent circuit to impedance spectra is proposed which allows us to uniquely separate bulk and interfacial elements. Moreover, the proposed method avoids overfitting of the bulk properties of the two liquids in contact and underfitting of the interfacial properties, as they might occur for standard one-step procedures. The key idea is to determine the bulk elements of the equivalent circuit in a first step by fitting corresponding subcircuits to the spectra of uniform electrolyte solutions, and afterwards fitting the full equivalent circuit with fixed bulk elements to the impedance spectrum containing the interface. This approach is exemplified for an equivalent circuit which leads to a physically intuitive qualitative behavior as well as to quantitatively realistic values of the interfacial elements. The proposed method is robust such that it can be expected to be applicable to a wide class of systems with liquid-liquid interfaces.