A new method for locating the global optimum : application of the cutting angle method to molecular structure prediction

Many problems in chemistry depend on the ability to identify the global minimum or maximum of a function. Examples include applications in chemometrics, optimization of reaction or operating conditions, and non-linear least-squares analysis. This paper presents the results of the application of a new method of deterministic global optimization, called the cutting angle method (CAM), as applied to the prediction of molecular geometries. CAM is shown to be competitive with other global optimization techniques for several benchmark molecular conformation problem. CAM is a general method that can also be applied to other computational problems involving global minima, global maxima or finding the roots of nonlinear equations.

The effect of hydrogenation on the ECAP compaction of Ti–6Al–4V powder and the mechanical properties of compacts

The effect of hydrogen content on the compaction of Ti–6Al–4V powder at low temperatures, namely 500 °C, using equal channel angular pressing (ECAP) with back pressure has been investigated. The properties of the compacts before and after a heat treatment and de-hydrogenation cycle have been determined. Compaction of powder by ECAP (500 °C and 260 MPa) has shown maximum levels of relative density of 99.3% and 99.4% when charged with 0.05–0.1 wt.% and 0.61–0.85 wt.% of hydrogen, respectively. After the de-hydrogenation heat treatment the diffusion bonding between individual powder particles was completed and the microstructure was altered, depending on the level of hydrogen content. Two local maxima of 99.2% and 98.1% were observed in the measured density of consolidated compacts for hydrogen contents between 0.05 wt.% and 0.1 wt.% and between 0.61 wt.% and 0.85 wt.%, respectively. However, the mechanical properties of the compacts within these two ranges of hydrogen content were significantly different due to a difference in the observed microstructure. An exceptionally high ductility of 29%, in combination with a relatively high strength of ~560 MPa, was measured in a shear punch test on specimens which had a prior hydrogen level of 0.05 wt.% before the heat treatment. It was shown that material consolidated from powder hydrogenated to low levels of hydrogen before compaction has the potential to offer substantial improvements in mechanical properties after a suitable heat treatment.

Chemistry, spectroscopy and analytical applications of certain chemiluminescent reactions

Chemiluminescence, the production of light from a chemical reaction, has found widespread use in analytical chemistry. Both tris (2, 2’-bipyridyl) ruthenium (II) and acidic potassium permanganate are chemiluminescence reagents that have been employed for the determination of a diverse range of analytes. This thesis encompasses some fundamental investigations into the chemistry and spectroscopy of these chemiluminescence reactions as well as extending the scope of their analytical applications. Specifically, a simple and robust capillary electrophoresis chemiluminescence detection system for the determination of codeine, O6-methylcodeine and thebaine is described, based upon the reaction of these analytes with chemically generated tris(2,2'-bipyridyl)ruthenium(III) prepared in sulfuric acid (0.05 M). The reagent solution was contained in a glass detection cell, which also held both the capillary and the cathode. The resultant chemiluminescence was monitored directly using a photomultiplier tube mounted flush against the base of the detection cell. The methodology, which incorporated a field amplification sample introduction procedure, realised detection limits (3a baseline noise) of 5 x 10~8 M for both codeine and O6-methylcodeine and 1 x 10~7 M for thebaine. The relative standard deviations of the migration times and the peak areas for the three analytes ranged from 2.2 % up to 2.5 % and 1.9 % up to 4.6 % respectively. Following minor instrumental modifications, morphine, oripavine and pseudomorphine were determined based upon their reaction with acidic potassium permanganate in the presence of sodium polyphosphate. To ensure no migration of the permanganate anion occurred, the anode was placed at the detector end whilst the electroosmotic flow was reversed by the addition of hexadimethrine bromide (0.001% m/v) to the electrolyte. The three analytes were separated counter to the electroosmotic flow via their interaction with a-cyclodextrin. The methodology realised detection limits (3 x S/N) of 2.5 x 10~7 M for both morphine and oripavine and 5 x 10~7 M for pseudomorphine. The relative standard deviations of the migration times and the peak heights for the three analytes ranged from 0.6 % up to 0.8 % and 1.5% up to 2.1 % respectively. Further improvements were made by incorporating a co-axial sheath flow detection cell. The methodology was validated by comparing the results realised using this technique with those obtained by high performance liquid chromatography (HPLC), for the determination of both morphine and oripavine in seven industrial process liquors. A complimentary capillary electrophoresis procedure with UV-absorption detection was also developed and applied to the determination of morphine, codeine, oripavine and thebaine in nine process liquors. The results were compared with those achieved using a standard HPLC method. Although over eighty papers have appeared in the literature on the analytical applications of acidic potassium permanganate chemiluminescence, little effort has been directed towards identifying the origin of the luminescence. It was found that chemiluminescence was generated during the manganese(III), manganese(IV) and manganese(VII) oxidations of sodium borohydride, sodium dithionite, sodium sulfite and hydrazine sulfate in acidic aqueous solution. From the corrected chemiluminescence spectra, the wavelengths of maximum emission were 689 ± 5 nm and 734 ± 5 nm when the reactions were performed in sodium hexametaphosphate and sodium dihydrogenorthophosphate or orthophosphoric acid environments respectively. The corrected phosphorescence spectrum of manganese(II) sulfate in a solution of sodium hexametaphosphate at 77 K, exhibited two peaks with maxima at 688 nm and 730 nm. The chemical and spectroscopic evidence presented strongly supported the postulation that the emission was an example of solution phase chemically induced phosphorescence of manganese(II). Thereby confirming earlier predictions that the chemiluminescence from acidic potassium permanganate reactions originated from an excited manganese(II) species. Additionally, these findings have had direct analytical application in that manganese(IV) was evaluated as a new reagent for chemiluminescence detection. The oxidations of twenty five organic and inorganic species, with solublised manganese(IV), were found to elicit analytically useful chemiluminescence with detection limits (3 x S/N) for Mn(II), Fe(II), morphine and codeine of 5 x 10-8 M, 2.5 x 10-7 M, 7.5 x 10-8 M and 5 x 10-8M, respectively. The corrected emission spectra from four different analytes gave wavelengths of maximum emission in the range from 733 nm up to 740 nm indicating that these chemiluminescence reactions also shared a common emitting species, excited manganese(II). Whilst several analytical problems were addressed in this thesis and answers to certain questions regarding the fundamentals of acidic potassium permanganate chemiluminescence were proposed, there are several areas that would benefit from further research. These are outlined in the final chapter of this thesis.

An nmr investigation of ionic structure and mobility in plasticized solid polymer electrolytes

²³Na and ¹⁹F nuclear magnetic resonance spectroscopy is used to investigate the effect of plasticizer addition on ionic structure and mobility in a urethane crosslinked polyether solid polymer electrolyte. The incorporation of dimethyl formamide and propylene carbonate plasticizers in a sodium triflate/polyether system results in an upfield chemical shift for the ²³Na resonance consistent with decreased anion-cation association and increased cation-plasticizer interactions. The ¹⁹F resonances appears less susceptible to changes in chemical environment with only minor chemical shift changes recorded. Spin lattice relaxation measurements for the ¹⁹F nucleus are also reported. Two minima are observed in the relaxation measurements consistent with both an inter and intramolecular relaxation mechanism.

Birth of a biome : insights into the assembly and maintenance of the Australian arid zone biota

The integration of phylogenetics, phylogeography and palaeoenvironmental studies is providing major insights into the historical forces that have shaped the Earth’s biomes. Yet our present view is biased towards arctic and temperate/tropical forest regions, with very little focus on the extensive arid regions of the planet. The Australian arid zone is one of the largest desert landform systems in the world, with a unique, diverse and relatively well-studied biota. With foci on palaeoenvironmental and molecular data, we here review what is known about the assembly and maintenance of this biome in the context of its physical history, and in comparison with other mesic biomes. Aridification of Australia began in the Mid-Miocene, around 15 million years, but fully arid landforms in central Australia appeared much later, around 1–4 million years. Dated molecular phylogenies of diverse taxa show the deepest divergences of arid-adapted taxa from the Mid-Miocene, consistent with the onset of desiccation. There is evidence of arid-adapted taxa evolving from mesicadapted ancestors, and also of speciation within the arid zone. There is no evidence for an increase in speciation rate during the Pleistocene, and most arid-zone species lineages date to the Pliocene or earlier. The last 0.8 million years have seen major fluctuations of the arid zone, with large areas covered by mobile sand dunes during glacial maxima. Some large, vagile taxa show patterns of recent expansion and migration throughout the arid zone, in parallel with the ice sheet-imposed range shifts in Northern Hemisphere taxa. Yet other taxa show high lineage diversity and strong phylogeographical structure, indicating persistence in multiple localised refugia over several glacial maxima. Similar to the Northern Hemisphere, Pleistocene range shifts have produced suture zones, creating the opportunity for diversification and speciation through hybridisation, polyploidy and parthenogenesis. This review highlights the opportunities that development of arid conditions provides for rapid and diverse evolutionary radiations, and re-enforces the emerging view that Pleistocene environmental change can have diverse impacts on genetic structure and diversity in different biomes. There is a clear need for more detailed and targeted phylogeographical studies of Australia’s arid biota and we suggest a framework and a set of a priori hypotheses by which to proceed.

Wavelets/multiwavelets bases and correspondence estimation problem : an analytic study

Correspondence estimation in one of the most active research areas in the field of computer vision and number of techniques has been proposed, possessing both advantages and shortcomings. Among the techniques reported, multiresolution analysis based stereo correspondence estimation has gained lot of research focus in recent years. Although, the most widely employed medium for multiresolution analysis is wavelets and multiwavelets bases, however, relatively little work has been reported in this context. In this work we have tried to address some of the issues regarding the work done in this domain and the inherited shortcomings. In the light of these shortcomings, we propose a new technique to overcome some of the flaws that could have significantly impact on the algorithm performance and has not been addressed in the earlier propositions. Proposed algorithm uses multiresolution analysis enforced with wavelets/multiwavelts transform modulus maxima to establish correspondences between the stereo pair of images. Variety of wavelets and multiwavelets bases, possessing distinct properties such as orthogonality, approximation order, short support and shape are employed to analyse their effect on the performance of correspondence estimation. The idea is to provide knowledge base to understand and establish relationships between wavelets and multiwavelets properties and their effect on the quality of stereo correspondence estimation.

Simultaneous control of spectroscopic and electrochemical properties in functionalised electrochemiluminescent tris(2,2'-bipyridine)ruthenium(II) complexes

Using a combination of electrochemical, spectroscopic and computational techniques, we have explored the fundamental properties of a series of ruthenium diimine complexes designed for coupling with other molecules or surfaces for electrochemiluminescence (ECL) sensing applications. With appropriate choice of ligand functionality, it is possible to manipulate emission wavelengths while keeping the redox ability of the complex relatively constant. DFT calculations show that in the case of electron withdrawing substituents such as ester or amide, the excited state is located on the substituted bipyridine ligand whereas in the case of alkyl functionality it is localised on a bipyridine. The factors that dictate annihilation ECL efficiency are interrelated. For example, the same factors that determine ΔG for the annihilation reaction (i.e. the relative energies of the HOMO and LUMO) have a corresponding effect on the energy of the excited state product. As a result, most of the complexes populate the excited state with an efficiency (Φex) of close to 80% despite the relatively wide range of emission maxima. The quantum yield of emission (Φp) and the possibility of competing side reactions are found to be the main determinants of ECL intensity.

Structuring in liquid alkanes between solid surfaces : force measurements and mean-field theory

Measurements have been made of the solvation forces between mica surfaces in the even-numbered n-alkanes from hexane to hexadecane. In all cases the force law is qualitatively very similar, characterized by a decaying oscillatory function of distance, as occurs for simple isotropic liquids. The spacing between successive minima in the force does not increase with carbon number, and is comparable to the width of a linear alkane molecule rather than its length or any average diameter. This suggests that the alkanes have some tendency towards a parallel orientation near the mica surfaces. The measurements give no indication of any strong repulsive component expected from mean-field theories of higher alkanes or polymers. The results of one such theory are presented, and the reasons for its failure to match the experimental data are discussed.

The Bassian Isthmus and the major ocean currents of southeast Australia influence the phylogeography and population structure of a southern Australian intertidal barnacle Catomerus polymerus (Darwin)

Southern Australia is currently divided into three marine biogeographical provinces based on faunal distributions and physical parameters. These regions indicate eastern and western distributions, with an overlap occurring in the Bass Strait in Victoria. However, studies indicate that the boundaries of these provinces vary depending on the species being examined, and in particular on the mode of development employed by that species, be they direct developers or planktonic larvae dispersers. Mitochondrial DNA sequence analysis of the surf barnacle Catomerus polymerus in southern Australia revealed an east–west phylogeographical split involving two highly divergent clades (cytochrome oxidase I 3.5 ± 0.76%, control region 6.7 ± 0.65%), with almost no geographical overlap. Spatial genetic structure was not detected within either clade, indicative of a relatively long-lived planktonic larval phase. Five microsatellite loci indicated that C. polymerus populations exhibit relatively high levels of genetic divergence, and fall into four subregions: eastern Australia, central Victoria, western Victoria and Tasmania, and South Australia. F_ST values between eastern Australia (from the eastern mitochondrial DNA clade) and the remaining three subregions ranged from 0.038 to 0.159, with other analyses indicating isolation by distance between the subregions of western mitochondrial origin. We suggest that the east–west division is indicative of allopatric divergence resulting from the emergence of the Bassian land-bridge during glacial maxima, preventing gene flow between these two lineages. Subsequently, contemporary ecological conditions, namely the East Australian, Leeuwin, and Zeehan currents and the geographical disjunctions at the Coorong and Ninety Mile Beach are most likely responsible for the four subregions indicated by the microsatellite data.

An improved Gbest guided artificial bee colony (IGGABC) algorithm for classification and prediction tasks

Artificial Neural Networks (ANN) performance depends on network topology, activation function, behaviors of data, suitable synapse's values and learning algorithms. Many existing works used different learning algorithms to train ANN for getting high performance. Artificial Bee Colony (ABC) algorithm is one of the latest successfully Swarm Intelligence based technique for training Multilayer Perceptron (MLP). Normally Gbest Guided Artificial Bee Colony (GGABC) algorithm has strong exploitation process for solving mathematical problems, however the poor exploration creates problems like slow convergence and trapping in local minima. In this paper, the Improved Gbest Guided Artificial Bee Colony (IGGABC) algorithm is proposed for finding global optima. The proposed IGGABC algorithm has strong exploitation and exploration processes. The experimental results show that IGGABC algorithm performs better than that standard GGABC, BP and ABC algorithms for Boolean data classification and time-series prediction tasks.

Wingbeat frequency and the body drag anomaly: wind-tunnel observations on a thrush nightingale (Luscinia Luscinia) and a teal (Anas crecca)

A teal (Anas crecca) and a thrush nightingale (Luscinia luscinia) were trained to fly in the Lund wind tunnel for periods of up to 3 and 16 h respectively. Both birds flew in steady flapping flight, with such regularity that their wingbeat frequencies could be determined by viewing them through a shutter stroboscope. When flying at a constant air speed, the teal's wingbeat frequency varied with the 0.364 power of the body mass and the thrush nightingale's varied with the 0.430 power. Both exponents differed from zero, but neither differed from the predicted value (0.5) at the 1 % level of significance. The teal continued to flap steadily as the tunnel tilt angle was varied from -1° (climb) to +6° (descent), while the wingbeat frequency declined progressively by about 11%. In both birds, the plot of wingbeat frequency against air speed in level flight was U-shaped, with small but statistically significant curvature. We identified the minima of these curves with the minimum power speed (Vmp) and found that the values predicted for Vmp, using previously published default values for the required variables, were only about two-thirds of the observed minimum-frequency speeds. The discrepancy could be resolved if the body drag coefficients (CDb) of both birds were near 0.08, rather than near 0.40 as previously assumed. The previously published high values for body drag coefficients were derived from wind-tunnel measurements on frozen bird bodies, from which the wings had been removed, and had long been regarded as anomalous, as values below 0.01 are given in the engineering literature for streamlined bodies. We suggest that birds of any size that have well-streamlined bodies can achieve minimum body drag coefficients of around 0.05 if the feet can be fully retracted under the flank feathers. In such birds, field observations of flight speeds may need to be reinterpreted in the light of higher estimates of Vmp. Estimates of the effective lift:drag ratio and range can also be revised upwards. Birds that have large feet or trailing legs may have higher body drag coefficients. The original estimates of around CDb=0.4 could be correct for species, such as pelicans and large herons, that also have prominent heads. We see no evidence for any progressive reduction of body drag coefficient in the Reynolds number range covered by our experiments, that is 21600-215 000 on the basis of body cross-sectional diameter.

Análise de modelos geológicos utilizando percolação dinâmica

In the present study we elaborated algorithms by using concepts from percolation theory which analyze the connectivity conditions in geological models of petroleum reservoirs. From the petrophysical parameters such as permeability, porosity, transmittivity and others, which may be generated by any statistical process, it is possible to determine the portion of the model with more connected cells, what the interconnected wells are, and the critical path between injector and source wells. This allows to classify the reservoir according to the modeled petrophysical parameters. This also make it possible to determine the percentage of the reservoir to which each well is connected. Generally, the connected regions and the respective minima and/or maxima in the occurrence of the petrophysical parameters studied constitute a good manner to characterize a reservoir volumetrically. Therefore, the algorithms allow to optimize the positioning of wells, offering a preview of the general conditions of the given model s connectivity. The intent is not to evaluate geological models, but to show how to interpret the deposits, how their petrophysical characteristics are spatially distributed, and how the connections between the several parts of the system are resolved, showing their critical paths and backbones. The execution of these algorithms allows us to know the properties of the model s connectivity before the work on reservoir flux simulation is started

Influência da dor na capacidade funcional de idosos institucionalizados

The aim of this study was to evaluate the pain influence regarding location, intensity and duration over functional capacity in institutionalized elderly (Fundacao Leur Brito). This is a descriptive exploratory study with a transversal design and quantitative approach. The population of the study was composed of 60 elderly, being 50% males with 60 years-old minimum age and 104 years-old maximum age, with mean age 77,6 (?}11,64) years-old. Data was collected by a structured query formulary divided in four parts: 1) Social, health and demographic characterization; 2) Pain related aspects (time and location); 3) Pain evaluation by numeric scale and 4) Functional capacity measured by Barthel Index. It was observed after evaluation by Squared-chi test (x2) statistical significant difference between pain presence and Barthel Index activities: bath (pvalue=0,015), dressing (p-value= 0,041), intimal hygiene transference (p-value=0,001), chair and bed transference (p-value=0,032), walking (p-value=0,010) and go upstairs (p-value=0,008). It was also observed statistical difference between total Barthel score (dependent/independent) and pain presence, p-value<0, 000. Through data obtained by this study, a multiprofessional approach is necessary to proper pain control and maintenance and/or regain of functional capacity, leading to an increase in life quality with more independence and autonomy to elderly

A field study to describe diel, tidal and semilunar rhythms of larval release in an assemblage of tropical rocky shore crabs

Available information on the larval release rhythms of brachyurans is biased to temperate estuarine species and outcomes resulting from some sort of artificial manipulation of ovigerous females. In this study we applied field methods to describe the larval release rhythms of an assemblage of tropical rocky shore crabs. Sampling the broods of ovigerous females of Pachygrapsus transversus at two different shores indicated a spatially consistent semilunar pattern, with larval release maxima around the full and new moon. Yet, synchronism between populations varied considerably, with the pattern obtained at the site exposed to a lower wave action far more apparent. Breeding cohorts at one of the sampled shores apparently belonged to actual age groups composing the ovigerous population. The data suggest that these breeding groups release their larvae in alternate syzygy periods, responding to a lunar cycle instead of the semilunar pattern observed for the whole population. For the description of shorter-term rhythms, temporal series at hour intervals were obtained by sampling the plankton and confinement boxes where ovigerous females were held. Unexpectedly, diurnal release activity prevailed over nocturnal hatching. Yet, only grapsids living higher on the shore exhibited strong preferences over the diel cycle, with P. transversus releasing their larvae during the day and Geograpsus lividus during the night. The pea crab Dissodactylus crinitichelis, the spider crab Epialtus brasiliensis and a suite of xanthoids undertook considerable releasing activity in both periods. Apart from the commensal pea crab D. crinitichelis, all other taxa revealed tide-related rhythms of larval release, with average estimates of the time of maximum hatching always around the time of high tides; usually during the flooding and slack, rather than the ebbing tide. Data obtained for P. transversus females held in confinement boxes indicated that early larval release is mostly due to nocturnal hatching, while zoeal release in diurnal groups took place at the time of high tide. Since nocturnal high tides at the study area occurred late, sometimes close to dusk, early release would allow more time for offshore transport of larvae when the action of potential predators is reduced.

Saccharomyces Cerevisiae cell wall dietary supplementation on the performance and intestinal mucosa development and integrity of broiler chickens vaccinated against coccidiosis

This study was carried out to verify if Saccharomyces cerevisiae cell wall (SCCW) dietary supplementation (0.2%) was capable of protecting the intestinal mucosa of broiler chickens vaccinated against coccidiosis. Body weight gain, feed intake, feed conversion and intestinal mucosa morphometric parameters and epithelial loss were evaluated. In the experiment,400 day-old male chicks were distributed according to a completely randomized design in a 2x2 factorial arrangement. The following treatments were applied: T1 - no vaccination/ no SCCW supplementation; T2 - no vaccination/SCCW supplementation; T3 - vaccination/no SCCW supplementation; and T4 - vaccination/SCCW supplementation to four replicates of 25 birds each. Birds were vaccinated on the first day of age using a spray vaccine (Coccivac B®, Coopers), containing E. acervulina, E. maxima, E. mivati and E. tenella. S. cerevisiae cell wall was supplied from the first day of age. Live performance, intestinal morphometric parameters and epithelial loss were evaluated at 14, 21 and 28 days of age. Performance was affected by vaccination only at 21-days of age, when body weight gain was reduced in the vaccinated birds, but no body weight difference was observed on day 28. Vaccine also increased the crypt depth (p<0.05) in the duodenum and jejunum, suggesting a high cell activity in the crypt:villus transition area to maintain the epithelial cell turnover. Villi number/area (103,269 µm²) was not affected (p>0.05) by vaccine or cell wall supplementation, and epithelial loss was more pronounced in the duodenum and jejunum. In conclusion, the findings of this study suggest that S. cerevisiae cell wall supplementation may be an useful management tool to maintain the intestinal integrity of broilers vaccinated against coccidiosis.