2-Butyl-4-iodoimidazole-5-carboxaldehyde: A Versatile Intermediate for the Synthesis of Highly Functionalized Imidazoles

The facile preparation of 2-butyl-4-iodoimidazole-5-carboxaldehyde 1 is described. The versatility of this intermediate in the synthesis of highly tunctionalized imidazoles is demonstrated with the synthesis of two potent and selective angiotensin II receptor antagonists.     

Speciation of metal(loid)s in environmental samples by X-ray absorption spectroscopy: A critical review

Element specificity is one of the key factors underlying the widespread use and acceptance of X-ray absorption spectroscopy (XAS) as a research tool in the environmental and geo-sciences. Independent of physical state (solid, liquid, gas), XAS analyses of metal(loid)s in complex environmental matrices over the past two decades have provided important information about speciation at environmentally relevant interfaces (e.g. solid–liquid) as well as in different media: plant tissues, rhizosphere, soils, sediments, ores, mineral process tailings, etc. Limited sample preparation requirements, the concomitant ability to preserve original physical and chemical states, and independence from crystallinity add to the advantages of using XAS in environmental investigations. Interpretations of XAS data are founded on sound physical and statistical models that can be applied to spectra of reference materials and mixed phases, respectively. For spectra collected directly from environmental matrices, abstract factor analysis and linear combination fitting provide the means to ascertain chemical, bonding, and crystalline states, and to extract quantitative information about their distribution within the data set. Through advances in optics, detectors, and data processing, X-ray fluorescence microprobes capable of focusing X-rays to micro- and nano-meter size have become competitive research venues for resolving the complexity of environmental samples at their inherent scale. The application of μ-XANES imaging, a new combinatorial approach of X-ray fluorescence spectrometry and XANES spectroscopy at the micron scale, is one of the latest technological advances allowing for lateral resolution of chemical states over wide areas due to vastly improved data processing and detector technology.     

Remarkable stereoselectivity switch in synthesis of carbonyl substituted N-arylamidrazones with low lipophilicity

Reaction of carbonyl substituted hydrazonoyl chlorides with amines usually leads to Z-configured amidrazone derivatives via nucleophilic substitution of the chlorine atom. Surprisingly, N,N-dimethylcarboxamide substituted hydrazonoyl chlorides yielded E-amidrazones when dialkylamines were used as nucleophilic reagent. The lipophilicities of the obtained amidrazones were found to be drastically reduced compared to their corresponding carboxanilides.     

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Time interval distributions of atoms in atomic beams

We report an experimental investigation of two-particle correlations between neutral atoms in a Hanbury Brown and Twiss experiment. Both an atom laser beam and a pseudo-thermal atomic beam are extracted from a Bose–Einstein condensate and the atom flux is measured with a single atom counter. We determine the conditional and the unconditional detection probabilities for the atoms in the beam and find good agreement with the theoretical predictions. PACS 03.75.Pp; 05.30.Jp; 07.77.Gx; 42.50.Pq     

Anticipative control of switched queueing systems

The relevant dynamics of a queueing process can be anticipated by taking future arrivals into account. If the transport from one queue to another is associated with transportation delays, as it is typical for traffic or productions networks, future arrivals to a queue are known over some time horizon and, thus, can be used for an anticipative control of the corresponding flows. A queue is controlled by switching its outflow between “on” and “off” similar to green and red traffic lights, where switching to “on” requires a non-zero setup time. Due to the presence of both continuous and discrete state variables, the queueing process is described as a hybrid dynamical system. From this formulation, we derive one observable of fundamental importance: the green time required to clear the queue. This quantity allows to detect switching time points for serving platoons without delay, i.e., in a “green wave” manner. Moreover, we quantify the cost of delaying the start of a service period or its termination in terms of additional waiting time. Our findings may serve as a basis for strategic control decisions.     

Multivariate analysis of spatially heterogeneous phase synchronisation in complex systems: application to self-organised control of material flows in networks

Networks of interacting components are a class of complex systems that has attracted considerable interest over the last decades. In particular, if the dynamics of the autonomous components is characterised by an oscillatory behaviour, different types of synchronisation can be observed in dependence on the type and strength of interactions. In this contribution, we study the transition from non-synchronised to synchronised phase dynamics in complex networks. The most common approach to quantify the degree of phase synchronisation in such systems is the consideration of measures of phase coherence which are averaged over all pairs of interacting components. However, this approach implicitly assumes a spatially homogeneous synchronisation process, which is typically not present in complex networks. As a potential alternative, two novel methods of multivariate phase synchronisation analysis are considered: synchronisation cluster analysis (SCA) and the linear variance decay (LVD) dimension method. The strengths and weaknesses of the traditional as well as both new approaches are briefly illustrated for a Kuramoto model with long-range coupling. As a practical application, we study how spatial heterogeneity influences the transition to phase synchronisation in traffic networks where intersecting material flows are subjected to a self-organised decentralised control. We find that the network performance and the degree of phase synchronisation are closely related to each other and decrease significantly in the case of structural heterogeneities. The influences of the different parameters of our control approach on the synchronisation process are systematically studied, yielding a sequence of Arnold tongues which correspond to different locking modes.     

Identifying complex periodic windows in continuous-time dynamical systems using recurrence-based methods

The identification of complex periodic windows in the two-dimensional parameter space of certain dynamical systems has recently attracted considerable interest. While for discrete systems, a discrimination between periodic and chaotic windows can be easily made based on the maximum Lyapunov exponent of the system, this remains a challenging task for continuous systems, especially if only short time series are available (e.g., in case of experimental data). In this work, we demonstrate that nonlinear measures based on recurrence plots obtained from such trajectories provide a practicable alternative for numerically detecting shrimps. Traditional diagonal line-based measures of recurrence quantification analysis as well as measures from complex network theory are shown to allow an excellent classification of periodic and chaotic behavior in parameter space. Using the well-studied Ro?ssler system as a benchmark example, we find that the average path length and the clustering coefficient of the resulting recurrence networks are particularly powerful discriminatory statistics for the identification of complex periodic windows.