Multistep electrochemical reduction path of clusters [Os3(CO)10(α-diimine)]: comparison of electrochemical and photochemical Os-Os(α-diimine) bond cleavage

Electrochemical reduction of the triangular clusters [Os-3(CO)(10)(alpha-dimine)] (alpha-dimine = 2,2'-bipyridine (bpy), 2,2'-bipyrimidine (bpym)) and [Os-3(CO)(10)(mu-bpym) ReBr(CO)(3)] produces primarily the corresponding radical anions. Their stability is strongly determined by the pi acceptor ability of the reducible alpha-dimine ligand, which decreases in the order mu-bpym > bpym >> bpy. Along this series, increasing delocalisation of the odd electron density in the radical anion over the Os(alpha-dimine) chelate ring causes weakening of the axial (CO)(4)Os-Os(CO)(2)(alpha-dimine) bond and its facile cleavage for alpha-diimine = bpy. In contrast, the cluster radical anion is inherently stable for the bridging bpym ligand, the strongest pi-acceptor in the studied series. In the absence of the partial delocalisation of the unpaired electron over the Re( bpym) chelate bond, the Os-3-core of the radical anion remains intact only at low temperatures. Subsequent one-electron reduction of [Os-3(CO)(10)(bpym)](center dot-) at T = 223 K gives the open-triosmium core (= Os-3*) dianion, [Os-3*(CO)(10)(bpym)](2-). Its oxidation leads to the recovery of parent [Os-3(CO)(10)( bpym)]. At room temperature, [Os-3*( CO)(10)(bpym)](2-) is formed along a two-electron (ECE) reduction path. The chemical step (C) results in the formation of an open- core radical anion that is directly reducible at the cathodic potential of the parent cluster in the second electrochemical (E) step. In weakly coordinating tetrahydrofuran, [Os-3*(CO)(10)( bpym)](2-) rapidly attacks yet non- reduced parent cluster molecules, producing the relatively stable open- core dimer [Os-3*(CO)(10)(bpym)](2)(2-) featuring two open- triangle cluster moieties connected with an ( bpym) Os - Os( bpym) bond. In butyronitrile, [Os-3*( CO)(10)(bpym)](2-) is stabilised by the solvent and the dimer [Os-3*(CO)(10)(bpym)](2)(2-) is then mainly formed by reoxidation of the dianion on reverse potential scan. The more reactive cluster [Os-3(CO)(10)(bpy)] follows the same reduction path, as supported by spectroelectrochemical results and additional valuable evidence obtained from cyclic voltammetric scans. The ultimate process in the reduction mechanism is fragmentation of the cluster core triggered by the reduction of the dimer [Os-3*(CO)(10)(alpha- diimine)](2)(2-). The products formed are [Os-2(CO)(8)](2-) and {Os(CO)(2)(alpha- diimine)}(2). The latter dinuclear fragments constitute a linear polymeric chain [Os( CO)(2)(alpha-dimine)] n that is further reducible at the alpha-dimine ligands. For alpha-dimine = bpy, the charged polymer is capable of reducing carbon dioxide. The electrochemical opening of the triosmium core in the [Os-3( CO)(10)(alpha-dimine)] clusters exhibits several common features with their photochemistry. The same Os-alpha-dimine bond dissociates in both cases but the intimate mechanisms are different.

Interference cancellation in two-path successive relay system with network coding

This paper proposes a novel interference cancellation algorithm for the two-path successive relay system using network coding. The two-path successive relay scheme was proposed recently to achieve full date rate transmission with half-duplex relays. Due to the simultaneous data transmission at the relay and source nodes, the two-path relay suffers from the so-called inter-relay interference (IRI) which may significantly degrade the system performance. In this paper, we propose to use the network coding to remove the IRI such that the interference is first encoded with the network coding at the relay nodes and later removed at the destination. The network coding has low complexity and can well suppress the IRI. Numerical simulations show that the proposed algorithm has better performance than existing approaches.

L1 transfer in the acquisition of manner and path in Spanish by native speakers of English

In this article the authors argue that L1 transfer from English is not only important in the early stages of L2 acquisition of Spanish, but remains influential in later stages if there is not enough positive evidence for the learners to progress in their development (Lefebvre, White, & Jourdan, 2006). The findings are based on analyses of path and manner of movement in stories told by British students of Spanish (N = 68) of three different proficiency levels. Verbs that conflate motion and path, on the one hand, are mastered early, possibly because the existence of Latinate path verbs, such as enter and ascend in English, facilitate their early acquisition by British learners of Spanish. Contrary to the findings of Cadierno (2004) and Cadierno and Ruiz (2006), the encoding of manner, in particular in boundary crossing contexts, seems to pose enormous difficulties, even among students who had been abroad on a placement in a Spanish-speaking country prior to the data collection. An analysis of the frequency of manner verbs in Spanish corpora shows that one of the key reasons why students struggle with manner is that manner verbs are so infrequent in Spanish. The authors claim that scarce positive evidence in the language exposed to and little or no negative evidence are responsible for the long-lasting effect of transfer on the expression of manner.

Path planning of robots in noisy workspaces using learning automata

The problem of a manipulator operating in a noisy workspace and required to move from an initial fixed position P0 to a final position Pf is considered. However, Pf is corrupted by noise, giving rise to Pˆf, which may be obtained by sensors. The use of learning automata is proposed to tackle this problem. An automaton is placed at each joint of the manipulator which moves according to the action chosen by the automaton (forward, backward, stationary) at each instant. The simultaneous reward or penalty of the automata enables avoiding any inverse kinematics computations that would be necessary if the distance of each joint from the final position had to be calculated. Three variable-structure learning algorithms are used, i.e., the discretized linear reward-penalty (DLR-P, the linear reward-penalty (LR-P ) and a nonlinear scheme. Each algorithm is separately tested with two (forward, backward) and three forward, backward, stationary) actions.

The investment development path in a globalised world: implications for Eastern Europe

This article summarises recent revisions to the investment development path (IDP) as postulated by Narula and Dunning (2010). The IDP provides a framework to understand the dynamic interaction between foreign direct investment (FDI) and economic development. The revisions take into account some recent changes in the global economic environment. This paper argues that studies based on the IDP should adopt a broader perspective, encompassing the idiosyncratic economic structure of countries as well as the heterogeneous nature of FDI. It is critical to understand the complex forces and interactions that determine the turning points in a country’s IDP, and to more explicitly acknowledge the role of historical, social and political circumstances in hindering or promoting FDI. We discuss some of the implications for Eastern European countries and provide some guidelines for future research.

Path dependence and Britain’s "coal wagon problem"

This article explores the nature and impact of path dependence in British rail coal haulage before 1939. It examines the factors which locked Britain's railways into a system of small coal wagons with highly fragmented ownership, the cost penalties of this system, and the reasons that attempts at modernization were unsuccessful. The analysis highlights the importance of decentralized ownership of a highly durable installed base of complementary infrastructure. Technical and institutional interrelatedness blocked incremental modernization, while the political requirement to compensate private wagon owners for the loss of their wagon stock made wholesale rationalization financially unattractive.

A novel satellite mission concept for upper air water vapour, aerosol and cloud observations using integrated path differential absorption LiDAR limb sounding

We propose a new satellite mission to deliver high quality measurements of upper air water vapour. The concept centres around a LiDAR in limb sounding by occultation geometry, designed to operate as a very long path system for differential absorption measurements. We present a preliminary performance analysis with a system sized to send 75 mJ pulses at 25 Hz at four wavelengths close to 935 nm, to up to 5 microsatellites in a counter-rotating orbit, carrying retroreflectors characterized by a reflected beam divergence of roughly twice the emitted laser beam divergence of 15 µrad. This provides water vapour profiles with a vertical sampling of 110 m; preliminary calculations suggest that the system could detect concentrations of less than 5 ppm. A secondary payload of a fairly conventional medium resolution multispectral radiometer allows wide-swath cloud and aerosol imaging. The total weight and power of the system are estimated at 3 tons and 2,700 W respectively. This novel concept presents significant challenges, including the performance of the lasers in space, the tracking between the main spacecraft and the retroreflectors, the refractive effects of turbulence, and the design of the telescopes to achieve a high signal-to-noise ratio for the high precision measurements. The mission concept was conceived at the Alpbach Summer School 2010.

Comparative study of the performance of the M-cycle counter-flow and cross-flow heat exchangers for indirect evaporative cooling - paving the path towards sustainable cooling of buildings

This paper provides a comparative study of the performance of cross-flow and counter-flow M-cycle heat exchangers for dew point cooling. It is recognised that evaporative cooling systems offer a low energy alternative to conventional air conditioning units. Recently emerged dew point cooling, as the renovated evaporative cooling configuration, is claimed to have much higher cooling output over the conventional evaporative modes owing to use of the M-cycle heat exchangers. Cross-flow and counter-flow heat exchangers, as the available structures for M-cycle dew point cooling processing, were theoretically and experimentally investigated to identify the difference in cooling effectiveness of both under the parallel structural/operational conditions, optimise the geometrical sizes of the exchangers and suggest their favourite operational conditions. Through development of a dedicated computer model and case-by-case experimental testing and validation, a parametric study of the cooling performance of the counter-flow and cross-flow heat exchangers was carried out. The results showed the counter-flow exchanger offered greater (around 20% higher) cooling capacity, as well as greater (15%–23% higher) dew-point and wet-bulb effectiveness when equal in physical size and under the same operating conditions. The cross-flow system, however, had a greater (10% higher) Energy Efficiency (COP). As the increased cooling effectiveness will lead to reduced air volume flow rate, smaller system size and lower cost, whilst the size and cost are the inherent barriers for use of dew point cooling as the alternation of the conventional cooling systems, the counter-flow system is considered to offer practical advantages over the cross-flow system that would aid the uptake of this low energy cooling alternative. In line with increased global demand for energy in cooling of building, largely by economic booming of emerging developing nations and recognised global warming, the research results will be of significant importance in terms of promoting deployment of the low energy dew point cooling system, helping reduction of energy use in cooling of buildings and cut of the associated carbon emission.

Cloud droplet size and liquid water path retrievals from zenith radiance measurements: examples from the Atmospheric Radiation Measurement Program and the Aerosol Robotic Network

The ground-based Atmospheric Radiation Measurement Program (ARM) and NASA Aerosol Robotic Net- work (AERONET) routinely monitor clouds using zenith ra- diances at visible and near-infrared wavelengths. Using the transmittance calculated from such measurements, we have developed a new retrieval method for cloud effective droplet size and conducted extensive tests for non-precipitating liquid water clouds. The underlying principle is to combine a liquid-water-absorbing wavelength (i.e., 1640 nm) with a non-water-absorbing wavelength for acquiring information on cloud droplet size and optical depth. For simulated stratocumulus clouds with liquid water path less than 300 g m−2 and horizontal resolution of 201 m, the retrieval method underestimates the mean effective radius by 0.8μm, with a root-mean-squared error of 1.7 μm and a relative deviation of 13%. For actual observations with a liquid water path less than 450 g m−2 at the ARM Oklahoma site during 2007– 2008, our 1.5-min-averaged retrievals are generally larger by around 1 μm than those from combined ground-based cloud radar and microwave radiometer at a 5-min temporal resolution. We also compared our retrievals to those from combined shortwave flux and microwave observations for relatively homogeneous clouds, showing that the bias between these two retrieval sets is negligible, but the error of 2.6 μm and the relative deviation of 22 % are larger than those found in our simulation case. Finally, the transmittance-based cloud effective droplet radii agree to better than 11 % with satellite observations and have a negative bias of 1 μm. Overall, the retrieval method provides reasonable cloud effective radius estimates, which can enhance the cloud products of both ARM and AERONET.