Spectroscopic properties and electronic structures of 17-electron half-sandwich ruthenium acetylide complexes, [Ru(CCAr)(L2)Cp′]+ (Ar=phenyl, p-tolyl, 1-naphthyl, 9-anthryl; L2=(PPh3)2, Cp′=Cp; L2=dppe; Cp′=Cp∗)

A series of half-sandwich bis(phosphine) ruthenium acetylide complexes [Ru(C CAr)(L-2)Cp'] (Ar = phenyl, p-tolyl, 1-naphthyl, 9-anthryl; L2 = (PPh3)(2), Cp' = Cp; L-2 = dppe; Cp' = Cp*) have been examined using electrochemical and spectroelectrochemical methods. One-electron oxidation of these complexes gave the corresponding radical cations [Ru(C CAr)(L2)Cp'](+). Those cations based on Ru(dppe)Cp*, or which feature a para-tolyl acetylide substituent, are more chemically robust than examples featuring the Ru(PPh3)(2)Cp moiety, permitting good quality UV-Vis-NIR and IR spectroscopic data to be obtained using spectroelectrochemical methods. On the basis of TD DFT calculations, the low energy (NIR) absorption bands in the experimental electronic spectra for most of these radical cations are assigned to transitions between the beta-HOSO and beta-LUSO, both of which have appreciable metal d and ethynyl pi character. However, the large contribution from the anthryl moiety to the frontier orbitals of [Ru(C CC14H9)(L2)CP'](+) suggests compounds containing this moiety should be described as metal-stabilised anthryl radical cations.

Molecular structures and electronic transitions of 3,6-Diphenyl-1,2-dithiin and its radical cation: a spectroelectrochemical and DFT study

One-electron oxidation of 3,6-diphenyl-1,2-dithiin yields the corresponding radical cation. The product is stable at low temperatures and can be distinguished by a triplet EPR signal. Cyclic voltammetric, UV-vis spectroelectrochemical, and DFT studies were performed to elucidate its molecular structure and electronic properties. Time-dependent DFT calculations reproduce appreciably well the UV-vis spectral changes observed during the oxidation. The results reveal a moderately twisted structure of the 1,2-dithiin heterocycle in the radical cation.

A comparison of stratosphere-troposphere transport in convection-permitting and convection-parameterizing simulations of three mesoscale convective systems

The transport of stratospheric air into the troposphere within deep convection was investigated using the Met Office Unified Model version 6.1. Three cases were simulated in which convective systems formed over the UK in the summer of 2005. For each of these three cases, simulations were performed on a grid having 4 km horizontal grid spacing in which the convection was parameterized and on a grid having 1 km horizontal grid spacing, which permitted explicit representation of the largest energy-containing scales of deep convection. Cross-tropopause transport was diagnosed using passive tracers that were initialized above the dynamically defined tropopause (2 potential vorticity unit surface) with a mixing ratio of 1. Although the synoptic-scale environment and triggering mechanisms varied between the cases, the total simulated transport was similar in all three cases. The total stratosphere-to-troposphere transport over the lifetime of the convective systems ranged from 25 to 100 kg/m2 across the simulated convective systems and resolutions, which corresponds to ∼5–20% of the total mass located within a stratospheric column extending 2 km above the tropopause. In all simulations, the transport into the lower troposphere (defined as below 3.5 km elevation) accounted for ∼1% of the total transport across the tropopause. In the 4 km runs most of the transport was due to parameterized convection, whereas in the 1 km runs the transport was due to explicitly resolved convection. The largest difference between the simulations with different resolutions occurred in the one case of midlevel convection considered, in which the total transport in the 1 km grid spacing simulation with explicit convection was 4 times that in the 4 km grid spacing simulation with parameterized convection. Although the total cross-tropopause transport was similar, stratospheric tracer was deposited more deeply to near-surface elevations in the convection-parameterizing simulations than in convection-permitting simulations.

Blind equalization of nonminimum phase channels: higher order cumulant based algorithm

Higher order cumulant analysis is applied to the blind equalization of linear time-invariant (LTI) nonminimum-phase channels. The channel model is moving-average based. To identify the moving average parameters of channels, a higher-order cumulant fitting approach is adopted in which a novel relay algorithm is proposed to obtain the global solution. In addition, the technique incorporates model order determination. The transmitted data are considered as independently identically distributed random variables over some discrete finite set (e.g., set {±1, ±3}). A transformation scheme is suggested so that third-order cumulant analysis can be applied to this type of data. Simulation examples verify the feasibility and potential of the algorithm. Performance is compared with that of the noncumulant-based Sato scheme in terms of the steady state MSE and convergence rate.

Synthesis, crystal structure and magnetic properties of three unprecedented tri-nuclear and one very rare tetra-nuclear copper(II) Schiff-base complexes supported by mixed azido/phenoxo/nitrato or acetato bridges

Three novel mixed bridged trinuclear and one tetranuclear copper(II) complexes of tridentate NNO donor Schiff base ligands [Cu-3(L-1)(2)(mu(LI)-N-3)(2)(CH3OH)(2)(BF2)(2)] (1), [Cu-3(L-1)(2)(mu(LI)-NO3-I kappa O.2 kappa O')(2)] (2), [Cu-3(L-2)(2)(mu(LI)-N-3)(2)(mu-NOI-I kappa O 2 kappa O')(2)] (3) and [Cu-4(L-3)(2)(mu(LI)-N-3)(4)(mu-CH3COO-I kappa O 2 kappa O')(2)] (4) have been synthesized by reaction of the respective tridentate ligands (L-1 = 2[1-(2-dimethylamino-ethylimino)-ethyl]-phenol, L-2 = 2[1-(2-diethylamino-ethylimino)-ethyl]-phenol, L-3 = 2-[1-(2-dimethylamino-ethylimino)-methyl]-phenol) with the corresponding copper(II) salts in the presence of NaN3 The complexes are characterized by single-crystal X-ray diffraction analyses and variable-temperature magnetic measurements Complex 1 is composed of two terminal [Cu(L-1)(mu(LI)-N-3)] units connected by a central [Cu(BF4)(2)] unit through nitrogen atoms of end-on azido ligands and a phenoxo oxygen atom of the tridentate ligand The structures of 2 and 3 are very similar, the only difference is that the central unit is [Cu(NO1)(2)] and the nitrate group forms an additional mu-NO3-I kappa O 2 kappa O' bridge between the terminal and central copper atoms In complex 4, the central unit is a di-mu(L1)-N-3 bridged dicopper entity, [Cu-2(mu(L1)-N-3)(2)(CH3COO)(2)] that connects two terminal [Cu(L-3)(mu(L1)-N-3)] units through end-on azido; phenoxo oxygen and mu-CH3COO-1 kappa O center dot 2 kappa O' triple bridges to result in a tetranuclear unit Analyses of variable-temperature magnetic susceptibility data indicates that there is a global weak antiferromagnetic interaction between the copper(II) ions in complexes 1-3, with the exchange parameter J of -9 86, -11 6 and -19 98 cm(-1) for 1-3, respectively In complex 4 theoretical calculations show the presence of an antiferromagnetic coupling in the triple bridging ligands (acetato, phenoxo and azido) while the interaction through the double end-on azido bridging ligand is strongly ferromagnetic.

Quantitative evaluation of three reconfiguration strategies on FPGAs: a case study

Reconfigurable computing is becoming an important new alternative for implementing computations. Field programmable gate arrays (FPGAs) are the ideal integrated circuit technology to experiment with the potential benefits of using different strategies of circuit specialization by reconfiguration. The final form of the reconfiguration strategy is often non-trivial to determine. Consequently, in this paper, we examine strategies for reconfiguration and, based on our experience, propose general guidelines for the tradeoffs using an area-time metric called functional density. Three experiments are set up to explore different reconfiguration strategies for FPGAs applied to a systolic implementation of a scalar quantizer used as a case study. Quantitative results for each experiment are given. The regular nature of the example means that the results can be generalized to a wide class of industry-relevant problems based on arrays.

Cross-cultural comparison of three medicinal floras and implications for bioprospecting strategies

Ethnopharmacological relevance One of the major drawbacks of using ethnomedicinal data to direct testing of plants which may find pharmaceutical use is that certain plants without bioactivity might be traditionally used. An accepted way of highlighting bioactive plants is to compare usage in different cultures. This approach infers that presumed independent discovery by different cultures provides evidence for bioactivity. Although several studies have made cross-cultural comparisons, they focussed on closely related cultures, where common patterns might be the result of common cultural traditions. The aim of this study was to compare three independent ethnomedicinal floras for which similarities can be more robustly interpreted as independent discoveries, and therefore likely to be indication for efficacy. Materials and methods Data from the literature were compiled about the ethnomedicinal floras for three groups of cultures (Nepal, New Zealand and the Cape of South Africa), selected to minimise historical cultural exchange. Ethnomedicinal applications were divided in 13 categories of use. Regression and binomial analyses were performed at the family level to highlight ethnomedicinal “hot” families. General and condition-specific analyses were carried out. Results from the three regions were compared. Results Several “hot” families (Anacardiaceae, Asteraceae, Convolvulaceae, Clusiaceae, Cucurbitaceae, Euphorbiaceae, Geraniaceae, Lamiaceae, Malvaceae, Rubiaceae, Sapindaceae, Sapotaceae and Solanaceae) were recovered in common in the general analyses. Several families were also found in common under different categories of use. Conclusions Although profound differences are found in the three ethnomedicinal floras, common patterns in ethnomedicinal usage are observed in widely disparate areas of the world with substantially different cultural traditions. As these similarities are likely to stem from independent discoveries, they strongly suggest that underlying bioactivity might be the reason for this convergent usage. The global distribution of prominent usage of families used in common obtained by this study and the wider literature is strong evidence that these families display exceptional potential for discovery of previously overlooked or new medicinal plants and should be placed in high priority in bioscreening studies and conservation schemes.

Temperature optimization of optical-phase conjugation in dye doped polymer-films

Experimental results of the temperature dependence of the nonlinear optical response of methyl red doped polymethylmethacrylate films in the range 20°C to 170°C are reported. It is found that the intensity of the phase conjugate signal resulting from degenerate four-wave mixing using pump and probe beams with parallel polarisation states increases dramatically on heating by a factor of ∼ 10, reaching a maximum at ∼ 100°C. The intensity of the phase conjugate signal for the case with crossed polarisation states of the pump and probe beams drops monotonically with increasing temperature. For both configurations the response time shortens with increasing temperature. The particular role of the polymer matrix in this temperature variation of the nonlinear optical response is discussed.

Tillage and herbicide treatments with inter-row cultivation influence weed densities and yield of three industrial crops

Field experiments were conducted in northern Greece in 2003 and 2004 to evaluate effects of tillage regimes (moldboard plowing, chisel plowing, and rotary tilling), cropping sequences(continuous cotton, cotton-sugar beet rotation,and continuous tobacco) and herbicide treatments with inter-row hand hoeing on weed population densities. Total weed densities were not affected by tillage treatment except that of barnyardgrass (Echinochloa crus-galli), which increased only in moldboard plowing treated plots during 2003. Redroot pigweed (Amaranthus retroflexus)and black nightshade (Solanum nigrum) densities were reduced in continuous cotton, while purple nutsedge (Cyperus rotundus), E. crus-galli, S. nigrum, and johnsongras(Sorghum halepense) densities were reduced in tobacco. A. retroflexus and S. nigrum were effectively controlled by all herbicide treatments with inter-row hand hoeing,whereas E. crus-galli was effectively reduced by herbicides applied to cotton and tobacco. S. halepense density reduction was a result of herbicide applied to tobacco with inter-row hand hoeing. Yield of all crops was higher under moldboard plowing and herbicide treatments. Pre-sowing and pre-emergence herbicide treatments in cotton and pre-transplant in tobacco integrated with inter-row cultivation resulted in efficient control of annual weed species and good crop yields. These observations are of practical relevance to crop selection by farmers in order to maintain weed populations at economically acceptable densities through the integration of various planting dates, sustainable herbicide use and inter-row cultivation; tools of great importance in integrated weed management systems. Keywords: cropping sequence, herbicide, integrated weed management, inter-row cultivation,tillage.

Validation of three new measure-correlate-predict models for the long-term prospection of the wind resource

The estimation of the long-term wind resource at a prospective site based on a relatively short on-site measurement campaign is an indispensable task in the development of a commercial wind farm. The typical industry approach is based on the measure-correlate-predict �MCP� method where a relational model between the site wind velocity data and the data obtained from a suitable reference site is built from concurrent records. In a subsequent step, a long-term prediction for the prospective site is obtained from a combination of the relational model and the historic reference data. In the present paper, a systematic study is presented where three new MCP models, together with two published reference models �a simple linear regression and the variance ratio method�, have been evaluated based on concurrent synthetic wind speed time series for two sites, simulating the prospective and the reference site. The synthetic method has the advantage of generating time series with the desired statistical properties, including Weibull scale and shape factors, required to evaluate the five methods under all plausible conditions. In this work, first a systematic discussion of the statistical fundamentals behind MCP methods is provided and three new models, one based on a nonlinear regression and two �termed kernel methods� derived from the use of conditional probability density functions, are proposed. All models are evaluated by using five metrics under a wide range of values of the correlation coefficient, the Weibull scale, and the Weibull shape factor. Only one of all models, a kernel method based on bivariate Weibull probability functions, is capable of accurately predicting all performance metrics studied.

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.

The coupled δ13C-radiocarbon systematics of three Late Glacial/early Holocene speleothems: insights into soil and caveprocesses at climatic transitions

The coupled δ13C-radiocarbon systematics of threeEuropean stalagmites deposited during the Late Glacial and early Holocene were investigated to understand better how the carbon isotope systematics of speleothems respond to climate transitions. The emphasis is on understanding how speleothems may record climate-driven changes in the proportions of biogenic (soil carbon) and limestone bedrock derived carbon. At two of the three sites, the combined δ13C and 14C data argue against greater inputs of limestone carbon as the sole cause of the observed shift to higher δ13C during the cold Younger Dryas. In these stalagmites (GAR-01 from La Garma cave, N. Spain and So-1 from Sofular cave, Turkey), the combined changes in δ13C and initial 14C activities suggest enhanced decomposition of old stored, more recalcitrant, soil carbon at the onset of the warmer early Holocene. Alternative explanations involving gradual temporal changes between open- and closed-system behaviour during the Late Glacial are difficult to reconcile with observed changes in speleothem δ13C and the growth rates. In contrast, a stalagmite from Pindal cave (N. Spain) indicates an abrupt change in carbon inputs linked to local hydrological and disequilibrium isotope fractionation effects, rather than climate change. For the first time, it is shown that while the initial 14C activities of all three stalagmites broadly follow the contemporaneous atmospheric 14C trends (the Younger Dryas atmospheric 14C anomaly can be clearly discerned), subtle changes in speleothem initial 14C activities are linked to climate-driven changes in soil carbon turnover at a climate transition.