Unraveling the electronic structures of low-valent naphthalene and anthracene iron complexes: x-ray, spectroscopic, and density functional theory studies

Naphthalene and anthracene transition metalates are potent reagents, but their electronic structures have remained poorly explored. A study of four Cp*-substituted iron complexes (Cp* = pentamethylcyclopentadienyl) now gives rare insight into the bonding features of such species. The highly oxygen- and water-sensitive compounds [K(18-crown- 6){Cp*Fe(η4-C10H8)}] (K1), [K(18-crown-6){Cp*Fe(η4-C14H10)}] (K2), [Cp*Fe(η4-C10H8)] (1), and [Cp*Fe(η4-C14H10)] (2) were synthesized and characterized by NMR, UV−vis, and 57Fe Mössbauer spectroscopy. The paramagnetic complexes 1 and 2 were additionally characterized by electron paramagnetic resonance (EPR) spectroscopy and magnetic susceptibility measurements. The molecular structures of complexes K1, K2, and 2 were determined by single-crystal X-ray crystallography. Cyclic voltammetry of 1 and 2 and spectroelectrochemical experiments revealed the redox properties of these complexes, which are reversibly reduced to the monoanions [Cp*Fe(η4-C10H8)]− (1−) and [Cp*Fe(η4-C14H10)]− (2−) and reversibly oxidized to the cations [Cp*Fe(η6-C10H8)]+ (1+) and [Cp*Fe(η6-C14H10)]+ (2+). Reduced orbital charges and spin densities of the naphthalene complexes 1−/0/+ and the anthracene derivatives 2−/0/+ were obtained by density functional theory (DFT) methods. Analysis of these data suggests that the electronic structures of the anions 1− and 2− are best represented by low-spin FeII ions coordinated by anionic Cp* and dianionic naphthalene and anthracene ligands. The electronic structures of the neutral complexes 1 and 2 may be described by a superposition of two resonance configurations which, on the one hand, involve a low-spin FeI ion coordinated by the neutral naphthalene or anthracene ligand L, and, on the other hand, a low-spin FeII ion coordinated to a ligand radical L•−. Our study thus reveals the redox noninnocent character of the naphthalene and anthracene ligands, which effectively stabilize the iron atoms in a low formal, but significantly higher spectroscopic oxidation state.

Review of R&D progress and practical application of the solar photovoltaic/thermal (PV/T) technologies

In this paper, the global market potential of solar thermal, photovoltaic (PV) and combined photovoltaic/thermal (PV/T) technologies in current time and near future was discussed. The concept of the PV/T and the theory behind the PV/T operation were briefly introduced, and standards for evaluating technical, economic and environmental performance of the PV/T systems were addressed. A comprehensive literature review into R&D works and practical application of the PV/T technology was illustrated and the review results were critically analysed in terms of PV/T type and research methodology used. The major features, current status, research focuses and existing difficulties/barriers related to the various types of PV/T were identified. The research methods, including theoretical analyses and computer simulation, experimental and combined experimental/theoretical investigation, demonstration and feasibility study, as well as economic and environmental analyses, applied into the PV/T technology were individually discussed, and the achievement and problems remaining in each research method category were described. Finally, opportunities for further work to carry on PV/T study were identified. The review research indicated that air/water-based PV/T systems are the commonly used technologies but their thermal removal effectiveness is lower. Refrigerant/heat-pipe-based PV/Ts, although still in research/laboratory stage, could achieve much higher solar conversion efficiencies over the air/water-based systems. However, these systems were found a few technical challenges in practice which require further resolutions. The review research suggested that further works could be undertaken to (1) develop new feasible, economic and energy efficient PV/T systems; (2) optimise the structural/geometrical configurations of the existing PV/T systems; (3) study long term dynamic performance of the PV/T systems; (4) demonstrate the PV/T systems in real buildings and conduct the feasibility study; and (5) carry on advanced economic and environmental analyses. This review research helps finding the questions remaining in PV/T technology, identify new research topics/directions to further improve the performance of the PV/T, remove the barriers in PV/T practical application, establish the standards/regulations related to PV/T design and installation, and promote its market penetration throughout the world.

Complexes of NiX2 (X=Cl− and NO3−) with a NNO donor Schiff base: anion dependent structural variations and spectroscopic behaviour

Two new nickel(11) complexes, [NiLL'(H2O)(2)Cl] (1) and [{NiLL'(H2O)](2)(mu-H)]NO3·H2O(2), have been synthesized using a tridentate Schiff base ligand, HL, 2-[(2-dimethylamino-ethylimino)-methyl]-phenol, along with Cl- or NO3(-) as an anionic co-ligand or counter anion (where L'H = salicylaldehyde). Both complexes have been characterized by X-ray crystallography. The structural analyses reveal that complex 1 is mononuclear whereas 2 is a hydrogen-bridged dinuclear complex. The Ni(II) ions possess a distorted octahedral geometry in both structures. Both complexes show negative solvatochromic behaviour with increasing donor number (DN) of the solvent. In more coordinating solvents, like DMSO or methanol, the colour of the solutions is green, whereas in less coordinating solvents, like dichloromethane (DCM) or acetonitrile, it is red.

Contested institutions? Traditional leaders and land access and control in communal areas of Eastern Cape Province, South Africa

The South African government has endeavoured to strengthen property rights in communal areas and develop civil society institutions for community-led development and natural resource management. However, the effectiveness of this remains unclear as the emergence and operation of civil society institutions in these areas is potentially constrained by the persistence of traditional authorities. Focusing on the former Transkei region of Eastern Cape Province, three case study communities are used examine the extent to which local institutions overlap in issues of land access and control. Within these communities, traditional leaders (chiefs and headmen) continue to exercise complete and sole authority over land allocation and use this to entrench their own positions. However, in the absence of effective state support, traditional authorities have only limited power over how land is used and in enforcing land rights, particularly over communal resources such as rangeland. This diminishes their local legitimacy and encourages some groups to contest their authority by cutting fences, ignoring collective grazing decisions and refusing to pay ‘fees’ levied on them. They are encouraged in such activities by the presence of democratically elected local civil society institutions such as ward councillors and farmers’ organisations, which have broad appeal and are increasingly responsible for much of the agrarian development that takes place, despite having no direct mandate over land. Where it occurs at all, interaction between these different institutions is generally restricted to approval being required from traditional leaders for land allocated to development projects. On this basis it is argued that a more radical approach to land reform in communal areas is required, which transfers all powers over land to elected and accountable local institutions and integrates land allocation, land management and agrarian development more effectively.

On the seasonal onset of polar mesospheric clouds and the breakdown of the stratospheric polar vortex in the Southern Hemisphere

Southern Hemisphere (SH) polar mesospheric clouds (PMCs), also known as noctilucent clouds, have been observed to be more variable and, in general, dimmer than their Northern Hemisphere (NH) counterparts. The precise cause of these hemispheric differences is not well understood. This paper focuses on one aspect of the hemispheric differences: the timing of the PMC season onset. Observations from the Aeronomy of Ice in the Mesosphere satellite indicate that in recent years the date on which the PMC season begins varies much more in the SH than in the NH. Using the Canadian Middle Atmosphere Model, we show that the generation of sufficiently low temperatures necessary for cloud formation in the SH summer polar mesosphere is perturbed by year‐to‐year variations in the timing of the late‐spring breakdown of the SH stratospheric polar vortex. These stratospheric variations, which persist until the end of December, influence the propagation of gravity waves up to the mesosphere. This adds a stratospheric control to the temperatures in the polar mesopause region during early summer, which causes the onset of PMCs to vary from one year to another. This effect is much stronger in the SH than in the NH because the breakdown of the polar vortex occurs much later in the SH, closer in time to the PMC season.

Model-measurement comparison of mesospheric temperature inversions, and a simple theory for their occurrence

Mesospheric temperature inversions are well established observed phenomena, yet their properties remain the subject of ongoing research. Comparisons between Rayleigh-scatter lidar temperature measurements obtained by the University of Western Ontario's Purple Crow Lidar (42.9°N, 81.4°W) and the Canadian Middle Atmosphere Model are used to quantify the statistics of inversions. In both model and measurements, inversions occur most frequently in the winter and exhibit an average amplitude of ∼10 K. The model exhibits virtually no inversions in the summer, while the measurements show a strongly reduced frequency of occurrence with an amplitude about half that in the winter. A simple theory of mesospheric inversions based on wave saturation is developed, with no adjustable parameters. It predicts that the environmental lapse rate must be less than half the adiabatic lapse rate for an inversion to form, and it predicts the ratio of the inversion amplitude and thickness as a function of environmental lapse rate. Comparison of this prediction to the actual amplitude/thickness ratio using the lidar measurements shows good agreement between theory and measurements.

Structure, conduct and the stochastic volatility of food markets: theory and empirics

The relationship between price volatility and competition is examined. Atheoretic, vector auto regressions on farm prices of wheat and retail prices of derivatives (flour, bread, pasta, bulgur and cookies) are compared to results from a dynamic, simultaneous-equations model with theory-based farm-to-retail linkages. Analytical results yield insights about numbers of firms and their impacts on demand- and supply-side multipliers, but the applications to Turkish time series (1988:1-1996:12) yield mixed results.

The evolutionary basis for differences between the immune systems of man, mouse, pig and ruminants

Studying the pathogenesis of an infectious disease like colibacillosis requires an understanding of the responses of target hosts to the organism both as a pathogen and as a commensal. The mucosal immune system constitutes the primary line of defence against luminal micro-organisms. The immunoglobulin-superfamily-based adaptive immune system evolved in the earliest jawed vertebrates, and the adaptive and innate immune system of humans, mice, pigs and ruminants co-evolved in common ancestors for approximately 300 million years. The divergence occurred only 100 mya and, as a consequence, most of the fundamental immunological mechanisms are very similar. However, since pressure on the immune system comes from rapidly evolving pathogens, immune systems must also evolve rapidly to maintain the ability of the host to survive and reproduce. As a consequence, there are a number of areas of detail where mammalian immune systems have diverged markedly from each other, such that results obtained in one species are not always immediately transferable to another. Thus, animal models of specific diseases need to be selected carefully, and the results interpreted with caution. Selection is made simpler where specific host species like cattle and pigs can be both target species and reservoirs for human disease, as in infections with Escherichia coli.

Reconstruction and prediction of variations in the open solar magnetic flux and interplanetary conditions

Historic geomagnetic activity observations have been used to reveal centennial variations in the open solar flux and the near-Earth heliospheric conditions (the interplanetary magnetic field and the solar wind speed). The various methods are in very good agreement for the past 135 years when there were sufficient reliable magnetic observatories in operation to eliminate problems due to site-specific errors and calibration drifts. This review underlines the physical principles that allow these reconstructions to be made, as well as the details of the various algorithms employed and the results obtained. Discussion is included of: the importance of the averaging timescale; the key differences between “range” and “interdiurnal variability” geomagnetic data; the need to distinguish source field sector structure from heliospherically-imposed field structure; the importance of ensuring that regressions used are statistically robust; and uncertainty analysis. The reconstructions are exceedingly useful as they provide calibration between the in-situ spacecraft measurements from the past five decades and the millennial records of heliospheric behaviour deduced from measured abundances of cosmogenic radionuclides found in terrestrial reservoirs. Continuity of open solar flux, using sunspot number to quantify the emergence rate, is the basis of a number of models that have been very successful in reproducing the variation derived from geomagnetic activity. These models allow us to extend the reconstructions back to before the development of the magnetometer and to cover the Maunder minimum. Allied to the radionuclide data, the models are revealing much about how the Sun and heliosphere behaved outside of grand solar maxima and are providing a means of predicting how solar activity is likely to evolve now that the recent grand maximum (that had prevailed throughout the space age) has come to an end.

Complex-valued b-spline neural networks for modelling and inverse of wiener systems

Communication signal processing applications often involve complex-valued (CV) functional representations for signals and systems. CV artificial neural networks have been studied theoretically and applied widely in nonlinear signal and data processing [1–11]. Note that most artificial neural networks cannot be automatically extended from the real-valued (RV) domain to the CV domain because the resulting model would in general violate Cauchy-Riemann conditions, and this means that the training algorithms become unusable. A number of analytic functions were introduced for the fully CV multilayer perceptrons (MLP) [4]. A fully CV radial basis function (RBF) nework was introduced in [8] for regression and classification applications. Alternatively, the problem can be avoided by using two RV artificial neural networks, one processing the real part and the other processing the imaginary part of the CV signal/system. A even more challenging problem is the inverse of a CV

Game-theoretic aspects of international mergers: Theory and case studies

This paper studies the exclusion of potential competition as a motivating factor for international mergers. We propose a simple game-theoretic framework in order to discuss the conditions under which mergers that prevent reciprocal domestic competition will occur. Our analysis highlights the shortcomings of antitrust policies based on pre-merger/post-merger concentration comparisons. A review of several recent European cases suggests that actual merger policy often fails to consider potential competition.

Assessing pragmatic interoperability of information systems from a semiotic perspective

Most of studies on interoperability of systems integration focus on technical and semantic levels, but hardly extend investigations on pragmatic level. Our past work has addressed pragmatic interoperability, which is concerned with the relationship between signs and the potential behaviour and intention of responsible agents. We also define the pragmatic interoperability as a level concerning with the aggregation and optimisation of various business processes for achieving intended purposes of different information systems. This paper, as the extension of our previous research, is to propose an assessment method for measuring pragmatic interoperability of information systems. We firstly propose interoperability analysis framework, which is based on the concept of semiosis. We then develop pragmatic interoperability assessment process from two dimensions including six aspects (informal, formal, technical, substantive, communication, and control). We finally illustrate the assessment process in an example.

Reliability comparison of transmit/receive diversity and error control coding in low-power medium access control protocols

Low-power medium access control (MAC) protocols used for communication of energy constraint wireless embedded devices do not cope well with situations where transmission channels are highly erroneous. Existing MAC protocols discard corrupted messages which lead to costly retransmissions. To improve transmission performance, it is possible to include an error correction scheme and transmit/receive diversity. It is possible to add redundant information to transmitted packets in order to recover data from corrupted packets. It is also possible to make use of transmit/receive diversity via multiple antennas to improve error resiliency of transmissions. Both schemes may be used in conjunction to further improve the performance. In this study, the authors show how an error correction scheme and transmit/receive diversity can be integrated in low-power MAC protocols. Furthermore, the authors investigate the achievable performance gains of both methods. This is important as both methods have associated costs (processing requirements; additional antennas and power) and for a given communication situation it must be decided which methods should be employed. The authors’ results show that, in many practical situations, error control coding outperforms transmission diversity; however, if very high reliability is required, it is useful to employ both schemes together.