Syntheses, structures and electrochemistry of some 1-(η-allylamino)-1-ferrocenylcarbene complexes of chromium(0), molybdenum(0) and tungsten(0) : Part 13: The chemistry of metallacyclic alkenylcarbene complexes

The metallacyclic complexes (OC)₄MC(η²-NHCH₂CHCHX)Fc (4; X = H) and (5; X = CH₂OH) [M = Cr: a; Mo: b; W: c; Fc = ferrocenyl = CpFe(C₅H₄)] were obtained in good yields upon photo-decarbonylation of the bimetallic allylaminocarbene complexes (OC)₅MC(NHCH₂CHCHX)Fc (2; X = H)/(3; X = CH₂OH). At room temperature complexes 2/3 exist as mixtures of E- and predominantly Z-isomers with regard to the C-N bond. The molecular structures of 4b and 4c were determined by X-ray diffraction analyses. The intermetallic communicative effects and the interplay of Fc and η²-alkene moieties of 4a and 4b were assessed by cyclovoltammetry. All complexes were also characterized in solution by one- and two-dimensional NMR spectroscopy (¹H, ¹³C, ¹H NOE, ¹H/¹H COSY, ¹³C/¹H HETCOR).     

A hyphenated flow-through analytical system for the study of the mobility and fractionation of trace and major elements in environmental solid samples

A flow-through hyphenated analytical method has been tested that enables not only the accelerated and efficient fractionation of trace elements (TE) species in environmental solids to be achieved but allows real-time studies on the leaching process to be made. Rotating coiled columns (RCC), earlier used mainly in countercurrent chromatography, have been successfully applied to the dynamic fractionation of heavy metals in soil, sediment, and sludge samples. A ground solid sample (about 0.5 g) was retained in a PTFE rotating column as the stationary phase whereas different aqueous eluents, chosen according to recent data on the selectivity of leachants, were continuously pumped through. Elements were determined in the effluent on-line by inductively coupled plasma atomic emission spectrometry (ICP-AES). Since the flow rates used in the RCC are in good agreement with those needed for cross-flow nebulization in the ICP-AES spectrometer, both devices were coupled directly without any additional interface systems. Simultaneous investigation of the elution profiles of trace and major elements has made it possible to study the elements association in separated fractions and hence to prove the efficacy of extractants and their selectivity toward targeted mineralogical phases of samples. The close association of heavy metals with Mn oxides in the sediment and sludge samples was confirmed. The time-resolved dissolution of different organic complexes of metals was observed for the sediment sample. It was found that in sediment and sludge samples the dynamics of iron release under the action of Tamm's reagent is somewhat different from that of aluminium. In addition, the proposed method can also be applied to develop effective leaching schemes and in the analysis of environmental solids for risk assessment of their contaminants addressed to water quality and bioavailability.     

Chiral phosphinooxazolines with a pentamethylferrocene backbone--synthesis and use as ligands in asymmetric catalysis

Novel phosphinooxazolines, containing a unit of central and a unit of planar chirality in a matched case combination, have been successfully tested in the Pd-catalyzed asymmetric allylic substitution with cycloalkenyl acetates as substrates.     

Theoretical, spectroscopic, and mechanistic studies on transition-metal dinitrogen complexes: implications to reactivity and relevance to the nitrogenase problem

Dinitrogen complexes of transition metals exhibit different binding geometries of N2 (end-on terminal, end-on bridging, side-on bridging, side-on end-on bridging), which are investigated by spectroscopy and DFT calculations, analyzing their electronic structure and reactivity. For comparison, a bis(mu-nitrido) complex, where the N--N bond has been split, has been studied as well. Most of these systems are highly covalent, and have strong metal-nitrogen bonds. In the present review, particular emphasis is put on a consideration of the activation of the coordinated dinitrogen ligand, making it susceptible to protonation, reactions with electrophiles or cleavage. In this context, theoretical, structural, and spectroscopic data giving informations on the amount of charge on the N2 unit are presented. The orbital interactions leading to a charge transfer from the metals to the dinitrogen ligand and the charge distribution within the coordinated N2 group are analyzed. Correlations between the binding mode and the observed reactivity of N2 are discussed.     

Investigating directed influences between activated brain areas in a motor-response task using fMRI

Localization of cognitive processes is a strength of functional neuroimaging. However, information about functional interactions between brain areas is crucial for a deeper understanding of brain function. We applied vector autoregressive modeling in the context of Granger causality as a method to analyze directed connectivity in a standard event-related fMRI study using a simple auditory-motor paradigm. The basic idea is to use temporal information in stochastic time series of a brain region in order to predict signal time courses in other brain regions. Thus, we predicted that the method should demonstrate causal influence of the auditory cortex and the supplementary motor area (SMA) on primary motor cortex. Eleven right-handed healthy female subjects were instructed to press a ball with either their left or their right hand when hearing the command "left" or "right" in the scanner. Influence to the left motor cortex was found from bilateral auditory cortex as well as from the SMA in 9 of 11 subjects. Granger causality to the right motor cortex existed from bilateral auditory cortex in 5 and from SMA in 6 subjects. Granger causality to the SMA existed from right auditory cortex in 7 subjects and from left auditory cortex in 8 subjects. Our findings in a simple task show that even under suboptimal circumstances (a relatively long TR of 2440 ms), Granger causality can be a useful tool to explore effective connectivity. Temporally optimized scanning should increase that potential.     

Identified particle production in p+p, d+Au and Au+Au collisions at RHIC

Measurements of identified particle production with the PHENIX experiment at RHIC have reached a mature state, where a multitude of nuclear systems at different colliding energies have been studied. The discovery configurations of $\sqrt {s_{NN} } = 130$ and 200 GeV Au+Au collisions have now been supplemented by additional Au+Au and Cu+Cu configurations at various energies, along with baseline p+p and d+Au runs at $\sqrt {s_{NN} } = 130$ GeV. In this work we present a systematic study of the Cronin effect in d+Au collisions and recent results from p+p collisions. We then proceed to make a critical comparison of pion, kaon and proton production in heavy ion and baseline systems, and discuss the observed nuclear effects on hadron production.     

On the Support of Minimizers of Causal Variational Principles

A class of causal variational principles on a compact manifold is introduced and analyzed both numerically and analytically. It is proved under general assumptions that the support of a minimizing measure is either completely timelike, or it is singular in the sense that its interior is empty. In the examples of the circle, the sphere and certain flag manifolds, the general results are supplemented by a more detailed and explicit analysis of the minimizers. On the sphere, we get a connection to packing problems and the Tammes distribution. Moreover, the minimal action is estimated from above and below.     

Transverse free vibration of non uniform rotating Timoshenko beams with elastically clamped boundary conditions

In the present paper the Differential Quadrature Method, DQM, and the domain decomposition are used to carry out the free transverse vibration analysis of non-uniform multi-span rotating Timoshenko beams with perfect and not perfect boundary conditions. The cross section could vary in a continuous or discontinuous fashion along the beam length. The material of the beam could be different in each beam span. The influence of elastically clamped boundary conditions at hub end are studied and discussed. The effect of an arbitrary hub radius is considered. The governing differential equations of motion for rotating Timoshenko beams come from the derivation of Hamilton’s principle. The first six natural frequencies of vibration are obtained for many particular situations and for some of them the mode shapes are also available. The examples of applications of the method indicated its effectiveness. The results for particular cases are in excellent agreement with published results and results obtained by means of the finite element method.     

Characterization of pressure dynamics in an axisymmetric separating/reattaching flow using fast-responding pressure-sensitive paint

This collaborative work discusses the results of time-resolved pressure-sensitive paint measurements performed on a model of a generic spacecraft under sub- and transonic test conditions. It is shown that optical pressure measurements using an active layer from platinum?Cporphyrin complexes (PtTFPP) in combination with a polymer-ceramic base layer are able to measure dynamic flow phenomena in the trisonic wind tunnel facility up to sampling rates of 2?kHz. Low amplitude fluctuations in the order of 0.1?kPa were determined by means of this measurement technique. The buffet dynamics, as well as the spatial extent of the recirculation area in the near-wake, compare well with numerical predictions and PIV measurements. Furthermore, characteristic coherent pressure modes on the base were resolved, which were predicted by large-eddy simulations.