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This article discusses the challenges for providers of local public services to adapt to increasing marketization and competition in the public sector. Based on some empirical evidence from local government in Germany, the article describes different adaptive measures in the past and shows the legal restrictions to strengthening performance and particularly competitiveness. Furthermore, the article presents some findings from good practice cases of local service providers in Germany who have successfully exposed themselves to market mechanisms. Finally, the article discusses observed results of increased competitiveness in the local government sector, with special regard to quality, efficiency and public employment. The article concludes with describing necessary elements of a competitive regime for public services and with some general reflections about the role of competition in the public sector.
This paper presents a corpus-based approach to the meaning of verb phrase idioms and proposes a set of parameters for the systematic description of their meaning in different contexts. It also discusses polysemy and vagueness in relation to idioms and offers criteria for the operationalisation of this distinction.
We investigate the bifurcation structures in a two-dimensional parameter space (PS) of a parametrically excited system with two degrees of freedom both analytically and numerically. By means of the Renyi entropy of second order K-2, which is estimated from recurrence plots, we uncover that regions of chaotic behavior are intermingled with many complex periodic windows, such as shrimp structures in the PS. A detailed numerical analysis shows that, the stable solutions lose stability either via period doubling, or via intermittency when the parameters leave these shrimps in different directions, indicating different bifurcation properties of the boundaries. The shrimps of different sizes offer promising ways to control the dynamics of such a complex system.
Fast, three-dimensional polarization mapping in piezoelectric sensor cables was performed by means of the novel thermal-pulse tomography (TPT) technique with a lateral resolution of 200 mum. The active piezoelectric cable material (a copolymer of polyvinylidene fluoride with trifluoroethylene) was electrically poled with a point-to-cable corona discharge. A focused laser was employed to heat the opaque outer electrode, and the short-circuit current generated by the thermal pulse was used to obtain 3D polarization maps via the scale transformation method. The article describes the TPT technique as a fast non-destructive option for studying cylindrical geometries.
Life on the edge: hydrogen sulfide and the fish communities of a Mexican cave and surrounding waters
(2006)
Most eucaryotic organisms classified as living in an extreme habitat are invertebrates. Here we report of a fish living in a Mexican cave (Cueva del Azufre) that is rich in highly toxic H2S. We compared the water chemistry and fish communities of the cave and several nearby surface streams. Our study revealed high concentrations of H2S in the cave and its outflow (El Azufre). The concentrations of H2S reach more than 300 mu M inside the cave, which are acutely toxic for most fishes. In both sulfidic habitats, the diversity of fishes was heavily reduced, and Poecilia mexicana was the dominant species indicating that the presence of H2S has an all-or-none effect, permitting only few species to survive in sulfidic habitats. Compared to habitats without H2S, P. mexicana from the cave and the outflow have a significantly lower body condition. Although there are microhabitats with varying concentrations of H2S within the cave, we could not find a higher fish density in areas with lower concentrations of H2S. We discuss that P. mexicana is one of the few extremophile vertebrates. Our study supports the idea that extreme habitats lead to an impoverished species diversity.
A tailor-made horseradish peroxidase (HRP) bulk composite electrode was developed on the basis of pyrolyzed cobalt tetramethoxyphenylporphyrin (CoTMPP) by modifying pore size and surface area of the porous carbon material through varying amounts of iron oxalate and sulfur prior to pyrolyzation. The materials were used to immobilize horseradish peroxidase (HRP). These electrodes were characterized in terms of their efficiency to reduce hydrogen peroxide. The heterogeneous electron transfer rate constants of different materials were determined with the rotating disk electrode method and a k(S) (401 +/- 61 s(-1)) exceeding previously reported values for native HRP was found.
We analytically describe the complex scenario of homoclinic bifurcations in the Chua’s circuit. We obtain a general scaling law that gives the ratio between bifurcation parameters of different nearby homoclinic orbits. As an application of this theoretical approach, we estimate the number of higher order subsidiary homoclinic orbits that appear between two consecutive lower order subsidiary orbits. Our analytical finds might be valid for a large class of dynamical systems and are numerically confirmed in the parameter space of the Chua’s circuit.
Shilnikov homoclinic orbits are trajectories that depart from a fixed saddle-focus point, with specific eigenvalues, and return to it after an infinite amount of time (that is also true to time reversal evolution). That results in an orbit that is unstable and has an infinite period. These two main characteristics contribute in the hardness for its observation in a dynamical system as well as in nature. However, its presence reveals fundamental characteristics of the system involved, as the existence of unstable periodic orbits embedded in a chaotic set. Once the unstable periodic orbits give invariants quantities of this set,1 the Shilnikov homoclinic orbits are also related to the characteristics of the chaotic set. Their connection with the fundamental dynamical properties is verified in a wide variety of systems. A series of numerical and experimental investigations reveal how Shilnikov homoclinic orbits, in the vicinity of a chaotic attractor, determine its dynamical and topological properties.4 Thus, the Shilnikov orbits are related to the returning time of the trajectory of a CO2 laser,5 also to the topology of a glow-discharge system.6 Moreover, some class of spiking neurons are modeled by chaos governed by such orbits,7,8 and their presence are connected to the intermittence present in rabbit arteries.9 These orbits are shown to be behind the mechanism of noise-induced phenomena,10 and they are also responsible for the dynamics of an electrochemical oscillator.11 In this work, we contribute to the understanding of how Shilnikov homoclinic orbits appear on the parameter space of systems as the ones above mentioned, by showing that these orbits are not only distributed following an universal rule but also exist for large parameter variations. We then confirm our previsions in the Chua’s circuit system
The first step in the estimation of probabilistic seismic hazard in a region commonly consists of the definition and characterization of the relevant seismic sources. Because in low-seismicity regions seismicity is often rather diffuse and faults are difficult to identify, large areal source zones are mostly used. The corresponding hypothesis is that seismicity is uniformly distributed inside each areal seismic source zone. In this study, the impact of this hypothesis on the probabilistic hazard estimation is quantified through the generation of synthetic spatial seismicity distributions. Fractal seismicity distributions are generated inside a given source zone and probabilistic hazard is computed for a set of sites located inside this zone. In our study, the impact of the spatial seismicity distribution is defined as the deviation from the hazard value obtained for a spatially uniform seismicity distribution. From the generation of a large number of synthetic distributions, the correlation between the fractal dimension D and the impact is derived. The results show that the assumption of spatially uniform seismicity tends to bias the hazard to higher values. The correlation can be used to determine the systematic biases and uncertainties for hazard estimations in real cases, where the fractal dimension has been determined. We apply the technique in Germany (Cologne area) and in France (Alps).
First comparison of array-derived rotational ground motions with direct ring laser measurements
(2006)
Recently, ring laser technology has provided the first consistent observations of rotational ground motions around a vertical axis induced by earthquakes. "Consistent," in this context, implies that the observed waveforms and amplitudes are compatible with collocated recordings of translational ground motions. In particular, transverse accelerations should be in phase with rotation rate and their ratio proportional to local horizontal phase velocity assuming plane-wave propagation. The ring laser installed at the Fundamental station Wettzell in the Bavarian Forest, Southeast Germany, is recording the rotation rate around a vertical axis, theoretically a linear combination of the space derivatives of the horizontal components of motion. This suggests that, in principle, rotation can be derived from seismic-array experiments by "finite differencing." This has been attempted previously in several studies; however, the accuracy of these observations could never be tested in the absence of direct measurements. We installed a double cross-shaped array of nine stations from December 2003 to March 2004 around the ring laser instrument and observed several large earthquakes on both the ring laser and the seismic array. Here we present for the first time a comparison of array-derived rotations with direct measurements of rotations for ground motions induced by the M 6.3 Al Hoceima, Morocco, earthquake of 24 February 2004. With complete 3D synthetic seismograms calculated for this event we show that even low levels of noise may considerably influence the accuracy of the array-derived rotations when the minimum number of required stations (three) is used. Nevertheless, when using all nine stations, the overall fit between direct and array-derived measurements is surprisingly good (maximum correlation coefficient of 0.94).
We installed a dense, amphibious, temporary seismological network to study the seismicity and structure of the seismogenic zone in southern Chile between 37° and 39°S, the nucleation area of the great 1960 Chile earthquake. 213 local earthquakes with 14.754 onset times were used for a simultaneous inversion for the 1‐D velocity model and precise earthquake locations. Relocated artificial shots suggest an accuracy of the earthquake hypocenter of about 1 km (horizontally) and 500 m (vertically). Crustal events along trench‐parallel and transverse, deep‐reaching faults reflect the interseismic transpressional deformation of the forearc crust due to the subduction of the Nazca plate. The transverse faults seems to accomplish differential lateral stresses between subduction zone segments. Many events situated in an internally structured, planar seismicity patch at 20 to 40 km depth near the coast indicate a stress concentration at the plate's interface at 38°S which might in part be induced by the fragmented forearc structure.
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)
We study synchronization behavior in networks of coupled chaotic oscillators with heterogeneous connection degrees. Our focus is on regimes away from the complete synchronization state, when the coupling is not strong enough, when the oscillators are under the influence of noise or when the oscillators are nonidentical. We have found a hierarchical organization of the synchronization behavior with respect to the collective dynamics of the network. Oscillators with more connections (hubs) are synchronized more closely by the collective dynamics and constitute the dynamical core of the network. The numerical observation of this hierarchical synchronization is supported with an analysis based on a mean field approximation and the master stability function. (C) 2006 American Institute of Physics
Realistic networks display not only a complex topological structure, but also a heterogeneous distribution of weights in the connection strengths. Here we study synchronization in weighted complex networks and show that the synchronizability of random networks with a large minimum degree is determined by two leading parameters: the mean degree and the heterogeneity of the distribution of node's intensity, where the intensity of a node, defined as the total strength of input connections, is a natural combination of topology and weights. Our results provide a possibility for the control of synchronization in complex networks by the manipulation of a few parameters
Dynamical organization of connection weights is studied in scale-free networks of chaotic oscillators, where the coupling strength of a node from its neighbors develops adaptively according to the local synchronization property between the node and its neighbors. We find that when complete synchronization is achieved, the coupling strength becomes weighted and correlated with the topology due to a hierarchical transition to synchronization in heterogeneous networks. Importantly, such an adaptive process enhances significantly the synchronizability of the networks, which could have meaningful implications in the manipulation of dynamical networks
Recently, two different groups have reported independently that the mobility of field-effect transistors made from regioregular poly(3-hexylthiophene) (P3HT) increases strongly with molecular weight. Two different models were presented: one proposing carrier trapping at grain boundaries and the second putting emphasis on the conformation and packing of the polymer chains in the thin layers for different molecular weights. Here, we present the results of detailed investigations of powders and thin films of deuterated P3HT fractions with different molecular weight. For powder samples, gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and X-ray diffraction (XRD) were used to investigate the structure and crystallization behavior of the polymers. The GPC investigations show that all weight fractions possess a rather broad molecular weight distribution. DSC measurements reveal a strong decrease of the crystallization temperature and, most important, a significant decrease of the degree of crystallinity with decreasing molecular weight. To study the structure of thin layers in lateral and vertical directions, both transmission electron microscopy (TEM) and X-ray grazing incidence diffraction (GID) were utilized. These methods show that thin layers of the low molecular weight fraction consist of well-defined crystalline domains embedded in a disordered matrix. We propose that the transport properties of layers prepared from fractions of poly(3-hexylthiophene) with different molecular weight are largely determined by the crystallinity of the samples and not by the perfection of the packing of the chains in the individual crystallites
We present an approach to generate (multivariate) twin surrogates (TS) based on recurrence properties. This technique generates surrogates which correspond to an independent copy of the underlying system, i.e. they induce a trajectory of the underlying system starting at different initial conditions. We show that these surrogates are well suited to test for complex synchronisation and exemplify this for the paradigmatic system of Rossler oscillators. The proposed test enables to assess the statistical relevance of a synchronisation analysis from passive experiments which are typical in natural systems
The spin probes TEMPO, TEMPOL, and CAT-1 were used to investigate microviscosity and micropolarity of imidazolium based ionic liquids bearing either tetrafluoroborate or hexafluorophosphate as anions and a variation of the substitution at the imidazolium ion. The average rotational correlation times (r) obtained by complete simulation of the X-band ESR spectra of TEMPO, TEMPOL, and CAT-1 increase with increasing viscosity of the ionic liquid although no Stokes Einstein behavior is observed. This is caused by microviscosity effects of the ionic liquids shown by application of the Gierer-Wirtz theory. Interestingly, the jump of the probe molecule into the free volume of the ionic liquids is a nonactivated process. The hyperfine coupling constants (A(iso) (N-14)) of TEMPO and TEMPOL dissolved in the ionic liquids do not depend on the structure of the ionic liquids. The A(iso) (N-14) values show a micropolarity of the ionic liquids that is comparable with methylenchloride in case of TEMPO and with dimethylsulfoxide in case of TEMPOL. Micropolarity monitored by CAT-1 strongly depends on structural variation of the ionic liquid. CAT-1 dissolved in imidazolium salts substituted with shorter alkyl chains at the nitrogen atom exhibits a micropolarity comparable with dimethylsulfoxide. A significant lower micropolarity is found for imidazolium. salts bearing a longer alkyl substituent at the nitrogen atom or a methyl substituent at C-2. Copyright (c) 2006 John Wiley & Sons, Ltd
Context: Placental and circulatory soluble fms-like tyrosine kinase 1 (sFlt1) has proven to be elevated in pregnant women with preeclampsia, a disease characterized by hypertension, proteinuria, and endothelial dysfunction. Recent studies also demonstrated an autoantibody against the angiotensin II type 1 (AT1) receptor (AT1-AA) in that disease. Objective: Both factors are discussed as key players in the etiology of preeclampsia. However, it has not yet been clarified whether these two circulating factors correlate and whether synergy determines the severity of pathology. Design: AT1-AA was retrospectively determined by a bioassay and sFlt1 by an ELISA. Patients: Serum from second-trimester pregnancies with normal or abnormal uterine perfusion and in women at term with or without pregnancy pathology was analyzed. Results: Most of the preeclamptic patients were characterized by high sFlt1 levels and the presence of AT1-AA, although the agonistic effects of the antibody did not correlate with the sFlt1 concentrations (P = 0.85). Although AT1- AA was also detected in second-trimester pregnancies evidencing abnormal uterine perfusion without later pathology, sFlt1 was not significantly elevated in these pregnancies, compared with those with normal uterine perfusion. However, whereas women with abnormal perfusion and later pregnancy pathology did not differ in AT1-AA, compared with those with normal outcome, sFlt1 was significantly increased. Again, the two factors did not correlate (P = 0.15). Conclusions: We conclude that AT1-AA bioactivity and sFlt1 concentrations do not correlate, are not mutually dependent, and are thus probably involved in distinct pathogenetic mechanisms. Both factors in combination may not be causative for the early impaired trophoblast invasion and pathological uterine perfusion
Silicon (Si) is the second-most abundant element in the earth's crust. In the pedosphere, however, huge spans of Si contents occur mainly caused by Si redistribution in soil profiles and landscapes. Here, we summarize the current knowledge on the different pools and fluxes of Si in soils and terrestrial biogeosystems. Weathering and subsequent release of soluble Si may lead to (1) secondarily bound Si in newly formed Al silicates, (2) amorphous silica precipitation on surfaces of other minerals, (3) plant uptake, formation of phytogenic Si, and subsequent retranslocation to soils, (4) translocation within soil profiles and formation of new horizons, or (5) translocation out of soils (desilication). The research carried out hitherto focused on the participation of Si in weathering processes, especially in clay neoformation, buffering mechanisms for acids in soils or chemical denudation of landscapes. There are, however, only few investigations on the characteristics and controls of the low-crystalline, almost pure silica compounds formed during pedogenesis. Further, there is strong demand to improve the knowledge of (micro)biological and rhizosphere processes contributing to Si mobilization, plant uptake, and formation of phytogenic Si in plants, and release due to microbial decomposition. The contribution of the biogenic Si sources to Si redistribution within soil profiles and desilication remains unknown concerning the pools, rates, processes, and driving forces. Comprehensive studies considering soil hydrological, chemical, and biological processes as well as their interactions at the scale of pedons and landscapes are necessary to make up and model the Si balance and to couple terrestrial processes with Si cycle of limnic, fluvial, or marine biogeosystems
The Cenozoic Tian Shan is one of the preeminent examples of an intracontinental orogen. However, there remains a significant controversy over when deformation related to the India-Asia collision commenced and therefore how shortening within the mountains has been partitioned over time. One approach has been to look at the modem shortening rate as measured by geodetic studies, combined with estimates of the total shortening across the range and extrapolate backwards. This approach suggests that the onset of range construction was ca. 10 Ma [K.Y. Abdrakhmatov, S.A. Aldazhanov, B.H. Hager, M.W Hamburger, T.A. Herring, K.B. Kalabaev, K.B. Kalabayev, V.I. Makarov, P. Molnar, S.V Panasyuk, M.T. Prilepin, R.E. Reilinger, I.S. Sadybakasov, B.J. Souter, Y.A. Trapeznikov, V.Y. Tsurkov, A.V. Zubovich, Relatively recent construction of the Tien Shan inferred from GPS measurements of present-day crustal deformation rates, Nature 384 (6608) (1996) 450-453]. An alternate method is to determine the age of the onset of exhumation using thermochronology. We present 19 new apatite fission-track (AFT) results from the southwestern Chinese portion of the belt; this region represents the first area exhumed during the late Tertiary along a transect at ca. 76 degrees E. Exhumation commenced at the Oligocene-Miocene boundary (similar to 24 Ma) along the Maidan and Muziduke thrusts, which bound the southern side of the Kokshaal range. Subsequently, deformation propagated ca. 20 km south to the Kashi basin- bounding thrust (KBT), which was exhumed by no earlier than 18.9 +/- 3.3 Ma. Three detrital AFT samples from Plio- Pleistocene strata deposited ca. 20 km farther south contain fission track grain age peaks that young monotonically upwards from 20.9 + 7.0/- 5.3 Ma to 15.9 + 5.4/- 4.0 Ma with a fairly constant lag time of 16 to 18 Ma. These ages, combined with structural data, suggest that both the hanging wall and the footwall of the KBT experienced a renewed episode of exhumation during the latest Cenozoic. The discrepancy between the Late Oligocene-Miocene initiation of significant exhumation shown herein and the 10 Ma initiation estimate from geodesy suggests that the Tian Shan has undergone a complex Late Cenozoic shortening history. Assuming that the present shortening rate could account for the total amount of Cenozoic shortening in 10 Ma and realizing that shortening initiated at least 15 Myr earlier, we conclude that the shortening rate must have varied over time, possibly in pulsed-southward migrating events, and that the present rate may not reflect the average rate since initiation of range uplift. (c) 2006 Elsevier B.V. All rights reserved
Glucosinolates are a group of secondary metabolites that function as defense substances against herbivores and micro-organisms in the plant order Capparales. Indole glucosinolates (IGS), derivatives of tryptophan, may also influence plant growth and development. In Arabidopsis thaliana, indole-3-acetaldoxime (IAOx) produced from tryptophan by the activity of two cytochrome P450 enzymes, CYP79B2 and CYP79B3, serves as a precursor for IGS biosynthesis but is also an intermediate in the biosynthetic pathway of indole-3-acetic acid (IAA). Another cytochrome P450 enzyme, CYP83B1, funnels IAOx into IGS. Although there is increasing information about the genes involved in this biochemical pathway, their regulation is not fully understood. OBP2 has recently been identified as a member of the DNA-binding-with-one- finger (DOF) transcription factors, but its function has not been studied in detail so far. Here we report that OBP2 is expressed in the vasculature of all Arabidopsis organs, including leaves, roots, flower stalks and petals. OBP2 expression is induced in response to a generalist herbivore, Spodoptera littoralis, and by treatment with the plant signalling molecule methyl jasmonate, both of which also trigger IGS accumulation. Constitutive and inducible over- expression of OBP2 activates expression of CYP83B1. In addition, auxin concentration is increased in leaves and seedlings of OBP2 over-expression lines relative to wild-type, and plant size is diminished due to a reduction in cell size. RNA interference-mediated OBP2 blockade leads to reduced expression of CYP83B1. Collectively, these data provide evidence that OBP2 is part of a regulatory network that regulates glucosinolate biosynthesis in Arabidopsis
Olefin metathesis and isomerization : from undesired side reactions to useful synthetic methodology
(2006)
Conversion of ruthenium carbene complexes to ruthenium hydride complexes by organometallic transformations in situ opens up interesting synthetic perspectives. In this account the use of Grubbs' catalyst to synthesize pent-4- enals selectively from diallyl- and allyl homoallyl ethers and scope and limitations of a Tandem RCM-isomerization sequence for the synthesis of cyclic enol ethers are discussed. (c) 2006 Elsevier B.V. All rights reserved
Population-based methods for the genetic mapping of adaptive traits and the analysis of natural selection require that the population structure and demographic history of a species are taken into account. We characterized geographic patterns of genetic variation in the model plant Arabidopsis thaliana by genotyping 115 genome-wide single nucleotide polymorphism (SNP) markers in 351 accessions from the whole species range using a matrix-assisted laser desorption/ionization time-of-flight assay, and by sequencing of nine unlinked short genomic regions in a subset of 64 accessions. The observed frequency distribution of SNPs is not consistent with a constant-size neutral model of sequence polymorphism due to an excess of rare polymorphisms. There is evidence for a significant population structure as indicated by differences in genetic diversity between geographic regions. Accessions from Central Asia have a low level of polymorphism and an increased level of genome-wide linkage disequilibrium (LD) relative to accessions from the Iberian Peninsula and Central Europe. Cluster analysis with the structure program grouped Eurasian accessions into K=6 clusters. Accessions from the Iberian Peninsula and from Central Asia constitute distinct populations, whereas Central and Eastern European accessions represent admixed populations in which genomes were reshuffled by historical recombination events. These patterns likely result from a rapid postglacial recolonization of Eurasia from glacial refugial populations. Our analyses suggest that mapping populations for association or LD mapping should be chosen from regional rather than a species-wide sample or identified genetically as sets of individuals with similar average genetic distances
Graphical models applying partial coherence to multivariate time series are a powerful tool to distinguish direct and indirect interdependencies in multivariate linear systems. We carry over the concept of graphical models and partialization analysis to phase signals of nonlinear synchronizing systems. This procedure leads to the partial phase synchronization index which generalizes a bivariate phase synchronization index to the multivariate case and reveals the coupling structure in multivariate synchronizing systems by differentiating direct and indirect interactions. This ensures that no false positive conclusions are drawn concerning the interaction structure in multivariate synchronizing systems. By application to the paradigmatic model of a coupled chaotic Roessler system, the power of the partial phase synchronization index is demonstrated
Existing theoretical literature fails to explain satisfactorily the differences between the pay of workers who are covered by collective agreements and others who are not. This study aims at providing a model framework that is amenable to an analysis of this issue. Our general-equilibrium approach integrates a dual labor market and a two-sector product market. The results suggest that the so-called "union wage gap" is largely determined by the degree of centralization of the bargains and, to a somewhat lesser extent, by the expenditure share of the unionized sector's goods
New ferroelectrets were developed on the basis of foams from cyclo-olefin polymers and copolymers. The results obtained on the cyclo-olefin polymer foam demonstrate a significant improvement of the service temperature for ferroelectret transducer materials. Suitable compounding and preparation led to cyclo-olefin ferroelectrets with an electromechanical activity of around 15 pC/N, which is thermally stable at least up to 110 degrees C. The properties in sensor and actuator applications are strongly dependent on the processing parameters related to film-making, sensor and actuator preparation, gas content and electric charging. The processing window for the film stretching was very narrow compared to the earlier developed polypropylene ferroelectrets. The film porosity, softness and thus the electromechanical activity are adjusted by gas-diffusion expansion. The activity of the electromechanically operating sensors and actuators was increased by stacking several layers of cellular cyclo-olefin film. For applications such as flat loudspeakers, the foamed films are tuned by tensioning them on a support frame. Correct tensioning was essential also for reducing the distortion levels.
Homopolymers were prepared from diallylammonium monomers bearing 4-methylcoumarin and 4-cyanobiphenyl as fluorescent and mesogenic side groups, as well as their copolymers with diallyldimethylammonium chloride (DADMAC). Organic-inorganic hybrid films were electrostatically self-assembled via the layer-by-layer technique on silicon wafers and quartz plates from the chromophore-bearing polymers and an exfoliated synthetic hectorite. Photophysical studies performed in solution as well as in the self-assembled films demonstrated only a weak tendency for aggregation of the chromophores in the macromolecules. Moreover, assemblies made from the polymers carrying the cyanobiphenyl mesogen were found to exhibit a pronounced internal order
A new precursor route for the preparation of bulk oxides and thin films of bismuth vanadates is proposed. The method involves the thermal treatment under air and mild conditions of hybrid organic-inorganic precursors, made from a zwitterionic salt-free polymer matrix and selected inorganic species. Monoclinic BiVO4 was obtained in the form of bulk oxide by calcination of the powdered homogeneous hybrid materials at 600 degrees C, from precursors containing Bi and V in stoichiometric amounts. In the same way, thermodiffractometry studies performed on a hybrid material exhibiting a Bi/ V molar ratio of 2 revealed that the ionic conductor gamma-Bi4V2O11 phase can be stabilized under very soft thermal conditions (300 degrees C). Additionally, thin films of yellow monoclinic BiVO4 were for the first time fabricated, by thermal treatment of the same hybrid polymeric precursors deposited on quartz substrates by spin coating, using a layer- by-layer technique. The presence of the target phase at the surface of the plates was confirmed by X-ray diffraction as well as UV-vis measurements