Synthesis, structure and solution chemistry of mixed-ligand oxovanadium(IV) and oxovanadium(V) complexes incorporating tridentate ONO donor hydrazone ligands

In the title family, the ONO donor ligands are the acetylhydrazones of salicylaidehyde (H2L1) and 2-hydroxyacetophenone (H2L2) (general abbreviation, H2L). The reaction of bis(acetylacetonato)oxovanadium(IV) with a mixture of tridentate H2L and a bidentate NN donor [e.g., 2,2'-bipyridine(bpy) or 1,10-phenanthroline(phen), hereafter B] ligands in equimolar ratio afforded the tetravalent complexes of the type [(VO)-O-IV(L)(B)]; complexes (1)-(4) whereas, if B is replaced by 8-hydroxyquinoline(Hhq) (which is a bidentate ON donor ligand), the above reaction mixture yielded the pentavalent complexes of the type [(VO)-O-V(L)(hq)]; complexes (5) and (6). Aerial oxygen is most likely the oxidant (for the oxidation of V-IV -> V-V) in the synthesis of pentavalent complexes (5) and (6). [(VO)-O-IV(L)(B)] complexes are one electron paramagnetic and display axial EPR spectra, while the [(VO)-O-V(L)(hq)] complexes are diamagnetic. The X-ray structure of [(VO)-O-V(L-2)(hq)] (6) indicates that H2L2 ligand is bonded with the vanadium meridionally in a tridentate dinegative fashion through its phenolic-O, enolic-O and imine-N atoms. The general bond length order is: oxo < phenolato < enolato. The V-O (enolato) bond is longer than V-O (phenolato) bond by similar to 0.07 angstrom and is identical with V-O (carboxylate) bond. H-1 NMR spectrum of (6) in CDCl3 solution indicates that the binding nature in the solid state is also retained in solution. Complexes (1)(4) display two ligand-field transitions in the visible region near 820 and 480 nm in DMF solution and exhibit irreversible oxidation peak near +0.60 V versus SCE in DMSO solution, while complexes (5) and (6) exhibit only LMCT band near 535 nm and display quasi-reversible one electron reduction peak near -0.10 V versus SCE in CH2Cl2 solution. The VO3+-VO2+ E-1/2 values shift considerably to more negative values when neutral NN donor is replaced by anionic ON donor species and it also provides better VO3+ binding via phenolato oxygen. For a given bidentate ligand, E-1/2 increases in the order: (L-2)(2-) < (L-1)(2-). (c) 2004 Elsevier B.V. All rights reserved.

In vitro fermentation of chitosan derivatives by mixed cultures of human faecal bacteria

Stirred, pH controlled batch cultures were carried out with faecal inocula and various chitosans to investigate the fermentation of chitosan derivatives by the human gut flora. Changes in bacterial levels and short chain fatty acids were measured over time. Low, medium and high molecular weight chitosan caused a decrease in bacteroides, bifidobacteria, clostridia and lactobacilli. A similar pattern was seen with chitosan oligosaccharide (COS). Butyrate levels also decreased. A three-stage fermentation model of the human colon was used for investigation of the metabolism of COS. In a region representing the proximal colon, clostridia decreased while lactobacilli increased. In the region representing the transverse colon, bacteroides and clostridia increased. Distally a small increase in bacteroides occurred. Butyrate levels increased. Under the highly competitive conditions of the human colon, many members of the microflora, are unable to compete for chitosans of low, medium or high molecular weight. COS were more easily utilised and when added to an in vitro colonic model led to increased production of butyrate, but some populations of potentially detrimental bacteria also increased. (c) 2005 Elsevier Ltd. All rights reserved.

Laboratory measurements of the water vapor continuum in the 1200–8000 cm−1 region between 293 K and 351 K

Laboratory Fourier transform spectroscopy of pure water vapor and water vapor mixed with air has been conducted between 1200 and 8000 cm−1 and at temperatures between 293 and 351 K with the purpose of detecting and characterizing the water vapor continuum. The spectral features of the continuum within the major water absorption bands are presented and compared where possible to those from previous experimental studies and to the commonly used MT_CKD and CKD models. It was observed that in the main, both models adequately capture the general spectral form of the continuum; however, there were a number of exceptions. Overall, there is no evidence to indicate that MT_CKD is an improvement upon the older CKD model in these spectral regions. There was generally good agreement between our results and those of other experimental investigators. The general mathematical forms of the self-continuum temperature dependence, given by both Roberts et al. (1976) and CKD/MT_CKD, fit well to the experimental continuum in these spectral regions. However, the range of temperatures over which we made measurements is not sufficient to discriminate between these two forms or to exclude the possibility of other forms of temperature dependence being more appropriate. At the same time, the actual parameters currently used in CKD/MT_CKD to describe the temperature dependence in many spectral regions cannot reproduce the observed strong spectral variation in the temperature dependence. It has not been possible to make definitive conclusions about the magnitude of the continuum absorption in the far wings of the absorption bands investigated here.

Vegetation and environmental dynamics in the southern Black Sea region since 18 kyr BP derived from the marine core 22-GC3

Sediments from the Black Sea, a region historically dominated by forests and steppe landscapes, are a valuable source of detailed information on the changes in regional terrestrial and aquatic environments at decadal to millennial scales. Here we present multi-proxy environmental records (pollen, dinoflagellate cysts, Ca, Ti and oxygen isotope data) from the uppermost 305 cm of the core 22-GC3 (42°13.53′N, 36°29.55′E) collected from a water depth of 838 m in the southern part of the Black Sea in 2007. The records span the last ~ 18 kyr (all ages are given in cal kyr BP). The pollen data reveal the dominance of the Artemisia-steppe in the region, suggesting rather dry/cold environments ~ 18–14.5 kyr BP. Warming/humidity increase during melt-water pulses (~ 16.1–14.5 kyr BP), indicated by δ18O records from the 22-GC3 core sediment and from the Sofular Cave stalagmite, is expressed in more negative δ13C values from the Sofular Cave, usually interpreted as the spreading of C3 plants. The records representing the interstadial complex (~ 14.5–12.9 kyr BP) show an increase in temperature and moisture, indicated by forest development, increased primary productivity and reduced surface run-off, whereas the switch from primary terrigenous to primary authigenic Ca origin occurs ~ 500 yr later. The Younger Dryas cooling is clearly demonstrated by more negative δ13C values from the Sofular Cave and a reduction of pines. The early Holocene (11.7–8.5 kyr BP) interval reveals relatively dry conditions compared to the mostly moist and warm middle Holocene (8.5–5 kyr BP), which is characterized by the establishment of the species-rich warm mixed and temperate deciduous forests in the low elevation belt, temperate deciduous beech-hornbeam forests in the middle and cool conifer forest in upper mountain belt. The border between the early and middle Holocene in the vegetation records coincides with the opening of the Mediterranean corridor at ~ 8.3 kyr BP, as indicated by a marked change in the dinocyst assemblages and in the sediment lithology. Changes in the pollen assemblages indicate a reduction in forest cover after ~ 5 kyr BP, which was likely caused by increased anthropogenic pressure on the regional vegetation.

Analysis of incoherent scatter radar data from non-thermal F-region plasma

A procedure is presented for fitting incoherent scatter radar data from non-thermal F-region ionospheric plasma, using theoretical spectra previously predicted. It is found that values of the shape distortion factor D∗, associated with deviations of the ion velocity distribution from a Maxwellian distribution, and ion temperatures can be deduced (the results being independent of the path of iteration) if the angle between the line-of-sight and the geomagnetic field is larger than about 15–20°. The procedure can be used with one or both of two sets of assumptions. These concern the validity of the adopted model for the line-of-sight ion velocity distribution in the one case or for the full three-dimensional ion velocity distribution function in the other. The distribution function employed was developed to describe the line-of-sight velocity distribution for large aspect angles, but both experimental data and Monte Carlo simulations indicate that the form of the field-perpendicular distribution can also describe the distribution at more general aspect angles. The assumption of this form for the line-of-sight velocity distribution at a general aspect angle enables rigorous derivation of values of the one-dimensional, line-of-sight ion temperature. With some additional assumptions (principally that the field-parallel distribution is always Maxwellian and there is a simple relationship between the ion temperature anisotropy and the distortion of the field-perpendicular distribution from a Maxwellian), fits to data for large aspect angles enable determination of line-of-sight temperatures at all aspect angles and hence, of the average ion temperature and the ion temperature anisotropy. For small aspect angles, the analysis is restricted to the determination of the line-of-sight ion temperature because the theoretical spectrum is insensitive to non-thermal effects when the plasma is viewed along directions almost parallel to the magnetic field. This limitation is expected to apply to any realistic model of the ion velocity distribution function and its consequences are discussed. Fit strategies which allow for mixed ion composition are also considered. Examples of fits to data from various EISCAT observing programmes are presented.

MetUM-GOML: a near-globally coupled atmosphere–ocean-mixed-layer model

Well-resolved air–sea interactions are simulated in a new ocean mixed-layer, coupled configuration of the Met Office Unified Model (MetUM-GOML), comprising the MetUM coupled to the Multi-Column K Profile Parameterization ocean (MC-KPP). This is the first globally coupled system which provides a vertically resolved, high near-surface resolution ocean at comparable computational cost to running in atmosphere-only mode. As well as being computationally inexpensive, this modelling framework is adaptable– the independent MC-KPP columns can be applied selectively in space and time – and controllable – by using temperature and salinity corrections the model can be constrained to any ocean state. The framework provides a powerful research tool for process-based studies of the impact of air–sea interactions in the global climate system. MetUM simulations have been performed which separate the impact of introducing inter- annual variability in sea surface temperatures (SSTs) from the impact of having atmosphere–ocean feedbacks. The representation of key aspects of tropical and extratropical variability are used to assess the performance of these simulations. Coupling the MetUM to MC-KPP is shown, for example, to reduce tropical precipitation biases, improve the propagation of, and spectral power associated with, the Madden–Julian Oscillation and produce closer-to-observed patterns of springtime blocking activity over the Euro-Atlantic region.

Virtualization for cost-effective teaching of assembly language programming

A virtual system that emulates an ARM-based processor machine has been created to replace a traditional hardware-based system for teaching assembly language. The proposed virtual system integrates, in a single environment, all the development tools necessary to deliver introductory or advanced courses on modern assembly language programming. The virtual system runs a Linux operating system in either a graphical or console mode on a Windows or Linux host machine. No software licenses or extra hardware are required to use the virtual system, thus students are free to carry their own ARM emulator with them on a USB memory stick. Institutions adopting this, or a similar virtual system, can also benefit by reducing capital investment in hardware-based development kits and enable distance learning courses.

Mixed-phase cloud physics and Southern Ocean cloud feedback in climate models

Increasing optical depth poleward of 45° is a robust response to warming in global climate models. Much of this cloud optical depth increase has been hypothesized to be due to transitions from ice-dominated to liquid-dominated mixed-phase cloud. In this study, the importance of liquid-ice partitioning for the optical depth feedback is quantified for 19 Coupled Model Intercomparison Project Phase 5 models. All models show a monotonic partitioning of ice and liquid as a function of temperature, but the temperature at which ice and liquid are equally mixed (the glaciation temperature) varies by as much as 40 K across models. Models that have a higher glaciation temperature are found to have a smaller climatological liquid water path (LWP) and condensed water path and experience a larger increase in LWP as the climate warms. The ice-liquid partitioning curve of each model may be used to calculate the response of LWP to warming. It is found that the repartitioning between ice and liquid in a warming climate contributes at least 20% to 80% of the increase in LWP as the climate warms, depending on model. Intermodel differences in the climatological partitioning between ice and liquid are estimated to contribute at least 20% to the intermodel spread in the high-latitude LWP response in the mixed-phase region poleward of 45°S. It is hypothesized that a more thorough evaluation and constraint of global climate model mixed-phase cloud parameterizations and validation of the total condensate and ice-liquid apportionment against observations will yield a substantial reduction in model uncertainty in the high-latitude cloud response to warming.

Interannual-decadal variability of wintertime mixed layer depths in the North Pacific detected by an ensemble of ocean syntheses

The interannual-decadal variability of the wintertime mixed layer depths (MLDs) over the North Pacific is investigated from an empirical orthogonal function (EOF) analysis of an ensemble of global ocean reanalyses. The first leading EOF mode represents the interannual MLD anomalies centered in the eastern part of the central mode water formation region in phase opposition with those in the eastern subtropics and the central Alaskan Gyre. This first EOF mode is highly correlated with the Pacific decadal oscillation index on both the interannual and decadal time scales. The second leading EOF mode represents the MLD variability in the subtropical mode water (STMW) formation region and has a good correlation with the wintertime West Pacific (WP) index with time lag of 3 years, suggesting the importance of the oceanic dynamical response to the change in the surface wind field associated with the meridional shifts of the Aleutian Low. The above MLD variabilities are in basic agreement with previous observational and modeling findings. Moreover the reanalysis ensemble provides uncertainty estimates. The interannual MLD anomalies in the first and second EOF modes are consistently represented by the individual reanalyses and the amplitudes of the variabilities generally exceed the ensemble spread of the reanalyses. Besides, the resulting MLD variability indices, spanning the 1948–2012 period, should be helpful for characterizing the North Pacific climate variability. In particular, a 6-year oscillation including the WP teleconnection pattern in the atmosphere and the oceanic MLD variability in the STMW formation region is first detected.

An approximate dynamic programming approach for improving accuracy of lossy data compression by Bloom filters

Bloom filters are a data structure for storing data in a compressed form. They offer excellent space and time efficiency at the cost of some loss of accuracy (so-called lossy compression). This work presents a yes-no Bloom filter, which as a data structure consisting of two parts: the yes-filter which is a standard Bloom filter and the no-filter which is another Bloom filter whose purpose is to represent those objects that were recognised incorrectly by the yes-filter (that is, to recognise the false positives of the yes-filter). By querying the no-filter after an object has been recognised by the yes-filter, we get a chance of rejecting it, which improves the accuracy of data recognition in comparison with the standard Bloom filter of the same total length. A further increase in accuracy is possible if one chooses objects to include in the no-filter so that the no-filter recognises as many as possible false positives but no true positives, thus producing the most accurate yes-no Bloom filter among all yes-no Bloom filters. This paper studies how optimization techniques can be used to maximize the number of false positives recognised by the no-filter, with the constraint being that it should recognise no true positives. To achieve this aim, an Integer Linear Program (ILP) is proposed for the optimal selection of false positives. In practice the problem size is normally large leading to intractable optimal solution. Considering the similarity of the ILP with the Multidimensional Knapsack Problem, an Approximate Dynamic Programming (ADP) model is developed making use of a reduced ILP for the value function approximation. Numerical results show the ADP model works best comparing with a number of heuristics as well as the CPLEX built-in solver (B&B), and this is what can be recommended for use in yes-no Bloom filters. In a wider context of the study of lossy compression algorithms, our researchis an example showing how the arsenal of optimization methods can be applied to improving the accuracy of compressed data.

Sole infection by human metapneumovirus among children with radiographically diagnosed community-acquired pneumonia in a tropical region

Background Limited information is available on the role of human metapneumovirus (HMPV) as the unique pathogen among children hospitalized for community-acquired pneumonia (CAP) in a tropical region. Objective We aimed to describe HMPV infection among children with CAP investigating bacterial and viral co-infections. Patients and methods A prospective study was carried out in Salvador, North-East Brazil. Overall, 268 children aged <5 years hospitalized for CAP were enrolled. Human metapneumovirus RNA was detected in nasopharyngeal aspirates (NPA) by reverse transcription polymerase chain reaction. Sixteen other bacterial and viral pathogens were investigated by an expanded panel of laboratory methods. Chest X-ray taken on admission was read by an independent paediatric radiologist unaware of clinical information or the established aetiology. Results Human metapneumovirus RNA was detected in NPAs of 11 (4.1%) children, of which 4 (36%) had sole HMPV infection. The disease was significantly shorter among patients with sole HMPV infection in comparison with patients with mixed infection (4 +/- 1 versus 7 +/- 2 days, P = 0.03). Three of those four patients had alveolar infiltrates. Conclusion Sole HMPV infection was detected in children with CAP in Salvador, North-East Brazil. HMPV may play a role in the childhood CAP burden.

A numerical investigation of the atmosphere-ocean thermal contrast over the coastal upwelling region of Cabo Frio, Brazil

An one-dimensional atmospheric second order closure model, coupled to an oceanic mixed layer model, is used to investigate the short term variation of the atmospheric and oceanic boundary layers in the coastal upwelling area of Cabo Frio, Brazil (23 degrees S, 42 degrees 08`W). The numerical simulations were carried out to evaluate the impact caused by the thermal contrast between atmosphere and ocean on the vertical extent and other properties of both atmospheric and oceanic boundary layers. The numerical simulations were designed taking as reference the observations carried out during the passage of a cold front that disrupted the upwelling regime in Cabo Frio in July of 1992. The simulations indicated that in 10 hours the mechanical mixing, sustained by a constant background flow of 10 in s(-1), increases the atmospheric boundary layer in 214 in when the atmosphere is initially 2 K warmer than the ocean (positive thermal contrast observed during upwelling regime). For an atmosphere initially -2 K colder than the ocean (negative thermal contrast observed during passage of the cold front), the incipient thermal convection intensifies the mechanical mixing increasing the vertical extent of the atmospheric boundary layer in 360 in. The vertical evolution of the atmospheric boundary layer is consistent with the observations carried out in Cabo Frio during upwelling condition. When the upwelling is disrupted, the discrepancy between the simulated and observed atmospheric boundary layer heights in Cabo Frio during July of 1992 increases considerably. During the period of 10 hours, the simulated oceanic mixed layer deepens 2 in and 5.4 in for positive and negative thermal contrasts of 2 K and -2 K, respectively. In the latter case, the larger vertical extent of the oceanic mixed layer is due to the presence of thermal convection in the atmospheric boundary layer, which in turn is associated to the absence of upwelling caused by the passage of cold fronts in Cabo Frio.

Crop rotation scheduling with adjacency constraints

In this article we propose a 0-1 optimization model to determine a crop rotation schedule for each plot in a cropping area. The rotations have the same duration in all the plots and the crops are selected to maximize plot occupation. The crops may have different production times and planting dates. The problem includes planting constraints for adjacent plots and also for sequences of crops in the rotations. Moreover, cultivating crops for green manuring and fallow periods are scheduled into each plot. As the model has, in general, a great number of constraints and variables, we propose a heuristics based on column generation. To evaluate the performance of the model and the method, computational experiments using real-world data were performed. The solutions obtained indicate that the method generates good results.

Outer Trust-Region Method for Constrained Optimization

Given an algorithm A for solving some mathematical problem based on the iterative solution of simpler subproblems, an outer trust-region (OTR) modification of A is the result of adding a trust-region constraint to each subproblem. The trust-region size is adaptively updated according to the behavior of crucial variables. The new subproblems should not be more complex than the original ones, and the convergence properties of the OTR algorithm should be the same as those of Algorithm A. In the present work, the OTR approach is exploited in connection with the ""greediness phenomenon"" of nonlinear programming. Convergence results for an OTR version of an augmented Lagrangian method for nonconvex constrained optimization are proved, and numerical experiments are presented.

Adaptivity in programming languages

A programming style can be seen as a particular model of shaping thought or a special way of codifying language to solve a problem. An adaptive device is made up of an underlying formalism, for instance, an automaton, a grammar, a decision tree, etc., and an adaptive mechanism, responsible for providing features for self-modification. Adaptive languages are obtained by using some programming language as the device’s underlying formalism. The conception of such languages calls for a new programming style, since the application of adaptive technology in the field of programming languages suggests a new way of thinking. Adaptive languages have the basic feature of allowing the expression of programs which self-modifying through adaptive actions at runtime. With the adaptive style, programming language codes can be structured in such a way that the codified program therein modifies or adapts itself towards the needs of the problem. The adaptive programming style may be a feasible alternate way to obtain self-modifying consistent codes, which allow its use in modern applications for self-modifying code.