The effects of the polymerization temperature and of voltammetric cycling on the chain length and the resistivity of polypyrrole films are investigated. The studies provide further proof for the existence of at least two different types of polypyrrole, the so-called PPy I and PPy II. As the electropolymerization of conjugated systems in contrast to normal polymerization reactions is a fully activated process, the generation of these different types of PPy depends on experimental parameters such as temperature or formation potentials. UV-vis measurements demonstrate that PPy II comprises significantly shorter chains than PPy I (8-12 vs 32-64 units); moreover, film conductivity is found to increase with the fraction of PPy II. This fraction is changed via the polymerization temperature as well as by cyclic voltammetry, both of which can induce a metal-insulator transition. The counter-intuitive relationship between resistivity and chain length is interpreted in terms of disorder-dominated transport, in which the shorter chains of PPy II support the formation of delocalized electronic states, thereby increasing the localization length. Thus, our results are in agreement with recent broadband reflectivity measurements.

Abstract:The intention of the presented study is to gain a better understanding of the mechanisms that caused the bimodal rainfall-runoff responses which occurred up to the mid-1970s regularly in the Schäfertal catchment and vanished after the onset of mining activities. Understanding this process is a first step to understanding the ongoing hydrological change in this area. It is hypothesized that either subsurface stormflow, or fast displacement of groundwater could cause the second delayed peak. A top-down analysis of rainfall-runoff data, field observations as well as process modelling are combined within a rejectionistic framework. A statistical analysis is used to test whether different predictors, which characterize the forcing, near surface water content and deeper subsurface store, allow the prediction of the type of rainfall-runoff response. Regression analysis is used with generalized linear models as they can deal with non-Gaussian error distributions as well as a non-stationary variance. The analysis reveals that the dominant predictors are the pre-event discharge (proxy of state of the groundwater store) and the precipitation amount. In the field campaign, the subsurface at a representative hillslope was investigated by means of electrical resistivity tomography in order to identify possible strata as flow paths for subsurface stormflow. A low resistivity in approximately 4 m depth-either due to a less permeable layer or the groundwater surface-was detected. The former could serve as a flow path for subsurface stormflow. Finally, the physical-based hydrological model CATFLOW and the groundwater model FEFLOW are compared with respect to their ability to reproduce the bimodal runoff responses. The groundwater model is able to reproduce the observations, although it uses only an abstract representation of the hillslopes. Process model analysis as well as statistical analysis strongly suggest that fast displacement of groundwater is the dominant process underlying the bimodal runoff reactions.

No abstract

Unusual conductivity effects: Suitably functionalized dendrimers (see picture) are capable of forming truly covalent three‐dimensional networks with remarkably high conductivity on electrochemical doping. Depending on the charging level of the electroactive components used as building blocks for the dendrimer core and the perimeter, two separated regimes of electrical conductivity can be observed.

3,3'-Dimethoxy-2,2'-bipyrrole (1) and 4,4'-dimethoxy-2,2'-bipyrrole (2) were obtained in short sequences and good yields from N-benzyl-3-hydroxypyrrole-2,4-dicarboxylic acid. The key intermediate leading to 1 is an N-benzyl-3-methoxypyrrole, which is dimerized by lithiation and oxidation with NiCl(2). The formation of 2 is achieved by a classical Ullmann coupling of diethyl 1-benzyl-2-bromo-4-methoxypyrrole-3,5-dicarboxylate. The N-benzyl protection groups of 1 and 2 are cleaved under reducing conditions with sodium in liquid ammonia. Both isomeric bipyrroles are extremely sensitive toward air. Compound 1 has a very low oxidation potential of 0.09 V against AgCl but film formation hardly occurs. On the other hand, compound 2 with a potential of 0.35 V readily forms stable polypyrrole films with anodic waves at -0.51 and -0.35 V and a cathodic wave at -0.77 V, the lowest potential ever observed for a p-doped polymer.