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Crystal structures of four different di-aryl-1,3,4-oxadiazole compounds (aryl = 2-pyridyl-, 3-pyridyl-, 2-aminophenyl-, 3-aminophenyl-) are determined. Crystallization of di(2-pyridyl)-1,3,4-oxadiazole yielded monoclinic and triclinic polymorphs. The structures are characterized by the occurrence of pi-pi interactions. Additionally, in case of the aminophenyl compounds intra- as well as intermolecular hydrogen bonds are found that influence the packing motif as well. Since these molecules are often used as ligands in metal-organic complexes similarities and differences of the molecular conformation between the molecules in the pure crystals and that of the ligands in the complexes are discussed. (c) 2006 Elsevier B.V. All rights reserved.
Relaxation processes at the glass transition in polyamide 11: From rigidity to viscoelasticity
(2006)
Relaxation processes associated with the glass transition in nonferroelectric and ferroelectric polyamide (PA) 11 are investigated by means of differential scanning calorimetry, dynamic mechanical analysis, and dielectric relaxation spectroscopy (DRS) in order to obtain information about the molecular mobility within the amorphous phase. In particular, the effects of melt quenching, cold drawing, and annealing just below the melting region are studied with respect to potential possibilities and limitations for improving the piezoelectric and pyroelectric properties of PA 11. A relaxation map is obtained from DRS that shows especially the crossover region where the cooperative alpha relaxation and the local beta relaxation merge into a single high-temperature process. No fundamental difference between quenched, cold-drawn, and annealed films is found, though in the cold-drawn (ferroelectric) film the alpha relaxation is suppressed and slowed down, but it is at least partly recovered by subsequent annealing. It is concluded that there exists an amorphous phase in all structures, even in the cold-drawn film. The amorphous phase can be more rigid or more viscoelastic depending on preparation. Cold drawing not only leads to crystallization in a ferroelectric form but also to higher rigidity of the remaining amorphous phase. Annealing just below the melting region after cold drawing causes a stronger phase separation between the crystalline phase and a more viscoelastic amorphous phase.
How do diverse dynamical patterns arise from the topology of complex networks? We study synchronization dynamics in the cortical brain network of the cat, which displays a hierarchically clustered organization, by modeling each node (cortical area) with a subnetwork of interacting excitable neurons. We find that in the biologically plausible regime the dynamics exhibits a hierarchical modular organization, in particular, revealing functional clusters coinciding with the anatomical communities at different scales. Our results provide insights into the relationship between network topology and functional organization of complex brain networks.
The aliphatic anthracene compound 1 and the oligomeric anthracene 2 were synthesized. Thin films of 1 and 2 mixed with the sensitizers tetraphenylporphyrin (TPP) and methylene blue (MB) were irradiated with visible light in air. Upon formation of singlet oxygen, the anthracene units were converted quantitatively to the corresponding endoperoxides. Heating of the irradiated samples afforded the parent anthracenes with high yields. Here, we demonstrate that the kinetics and reversibility of this reaction strongly depend on the microenvironment of the anthracene groups in the two compounds. The photooxidation of thin films of I is accompanied by interesting changes in the morphology of the film and allows the first application of 1 as a nondestructive negative-tone photo-resist for lithography and as an oxidizing ink. The morphology of 2 remained unchanged after photooxidation as a result of the stabilizing oligomer backbone. This stabilizing effect significantly improves the photochromic performance of 2. The reversibility of the photooxidation is very high (> 90%) for oligomeric films of 2 after several cycles of irradiation and beating. Decomposition of the anthracene and a loss of the activity of the sensitizer diminish slightly the performance of the monomeric species.
Iterated finite state sequential transducers are considered as language generating devices. The hierarchy induced by the size of the state alphabet is proved to collapse to the fourth level. The corresponding language families are related to the families of languages generated by Lindenmayer systems and Chomsky grammars. Finally, some results on deterministic and extended iterated finite state transducers are established.
Pattern-process analysis is one of the main threads in landscape ecological research. It aims at understanding the complex relationships between ecological processes and landscape patterns, identifying the underlying mechanisms and deriving valid predictions for scenarios of landscape change and its consequences. Today, various studies cope with these tasks through so called "landscape modelling" approaches. They integrate different aspects of heterogeneous and dynamic landscapes and model different driving forces, often using both statistical and process-oriented techniques. We identify two main approaches to deal with the analysis of pattern-process interactions: the first starts with pattern detection, pattern description and pattern analysis, the second with process description, simulation and pattern generation. Focussing on the interplay between these two approaches, landscape analysis and landscape modelling will improve our understanding of pattern-process interactions. The comparison of simulated and observed pattern is a prerequisite for both approaches. Therefore, we identify a set of quantitative, robust, and reproducible methods for the analysis of spatiotemporal patterns that is a starting point for a standard toolbox for ecologists as major future challenge and suggest necessary further methodological developments. (c) 2006 Elsevier B.V. All rights reserved.
The overuse of rainforests in the last century and its consequences necessitate a rethinking of logging policies. To this end models have been developed to simulate rainforest dynamics and to allow optional management strategies to be evaluated. Parameterisation of presently existing models for a certain site needs a lot of work, thus the parameterisation effort is too high to apply the models to a wide range of rainforests. Hence, in this paper we introduce the simplified model FORREG using the knowledge we have gained from a more complex model, FORMIX3-Q. The FORREG model uses differential equations to determine the volume growth of three successional species groups. Parameterisation is simplified by a genetic algorithm, which determines the required internal model parameters from characteristics of the forest dynamics. The new model is employed to assess the sustainability of various logging policies in terms of yield and damage. Results for three forests are discussed: (1) the tropical lowland rain forest in the Deramakot Forest Reserve, (2) the Lambir National Park in Malaysia and (3) a subtropical forest in Paraguay. Our model reproduces both undisturbed forest dynamics and dynamics of logged forests simulated with FORMIX3-Q very well. However, the resultant volumes of yield and damage differ slightly from those gained by FORMIX3-Q if short logging cycles are simulated. Choosing longer logging cycles leads to a good correspondence of both models. For the Deramakot Forest Reserve different logging cycles are compared and discussed. (c) 2006 Elsevier B.V. All rights reserved.
Wetlands, and in particular riparian wetlands, represent an interface between the catchment area and the aquatic environment. They control the exchange of water and related chemical fluxes from the upper catchment area to surface waters like streams and lakes. Their influence on water and nutrient balances has been investigated mainly at the patch scale. In this study an attempt was made (a) to integrate riparian zones and wetlands into eco-hydrological river basin modelling, and (b) to quantify the impacts of riparian wetland processes on water and nutrient fluxes in a meso-scale catchment located in the northeastern German lowland. The investigation was performed by analysing hydro-chemical field data and applying the eco-hydrological model SWIM (Soil and Water Integrated Model), which was extended to reproduce the relevant water and nutrient flows and retention processes at the catchment scale in general, and in riparian zones and wetlands in particular. The main extensions introduced in the model were: (1) implementation of daily groundwater table dynamics at the hydrotope level, (2) implementation of water and nutrient uptake by plants from groundwater in riparian zones and wetlands, and (3) assessment of nutrient retention in groundwater and interflow. The simulation results indicate that wetlands, though they represent relatively small parts of the total catchment area, may have a significant impact on the overall water and nutrient balances of the catchment. The uncertainty of the simulation results is considerably high, with the main sources of uncertainty being the model parameters representing the geo-hydrology and the input data for land use management. (c) 2006 Elsevier B.V. All rights reserved.
Translational diffusion of fluorescent tracer molecules in azobenzene polymer layers is studied at different temperatures and under illumination using the method of fluorescence recovery after photobleaching. Diffusion is clearly observed in the dark above the glass transition temperature, while homogeneous illumination at 488 nm and 100 mW/cm(2) does not cause any detectable diffusion of the dye molecules within azobenzene layers. This implies that the viscosity of azobenzene layers remains nearly unchanged under illumination with visible light in the absence of internal or external forces. (c) 2006 American Institute of Physics.
We study the overdamped version of two coupled anharmonic oscillators under the influence of both low- and high-frequency forces respectively and a Gaussian noise term added to one of the two state variables of the system. The dynamics of the system is first studied in the presence of both forces separately without noise. In the presence of only one of the forces, no resonance behaviour is observed, however, hysteresis happens there. Then the influence of the high-frequency force in the presence of a low-frequency, i.e. biharmonic forcing, is studied. Vibrational resonance is found to occur when the amplitude of the high-frequency force is varied. The resonance curve resembles a stochastic resonance-like curve. It is maximum at the value of g at which the orbit lies in one well during one half of the drive cycle of the low-frequency force and in the other for the remaining half cycle. Vibrational resonance is characterized using the response amplitude and mean residence time. We show the occurrence of stochastic resonance behaviour in the overdamped system by replacing the high-frequency force by Gaussian noise. Similarities and differences between both types of resonance are presented. (c) 2006 Elsevier B.V. All rights reserved.
The results of a quantum-mechanical study of vibrational relaxation of hydrogen adsorbed on a Si(100) surface with the multi-configurational time-dependent Hartree (MCTDH) method are presented. A two-dimensional subsystem is coupled non-linearly to a bath of harmonic oscillators (phonons of the Si bulk), and the relaxation of subsystem vibrations proceeds primarily via a two-phonon process. Characteristic times of the system evolution agree well with our previous perturbation theory study. The vibrational population decay is non-exponential, exhibiting pronounced recurrences due to finite bath size. The dependence of the lifetimes of the vibrational levels on the bath size and on the coupling details is investigated.
The Enigma of Arrival
(2006)