Oxidation of mixed-valence CoIII/FeII complexes reversed at high pH: A kinetico-mechanistic study of water oxidation

The outer-sphere oxidation of Fell in the mixed-valence complex trans-[(LCoNCFeII)-Co-14S-N-III(CN)(6)](-), being L-14S an N3S2 macrocylic donor set on the cobalt(III) center, has been studied. The comparison with the known processes of N-5 macrocycle complexes has been carried out in view of the important differences occurring on the redox potential of the cobalt center. The results indicate that the outer-sphere oxidation reactions with S2O82- and [Co(ox)(3)](3-) involve a great amount of solvent-assisted hydrogen bonding that, as a consequence from the change from two amines to sulfur donors, are more restricted. This is shown by the more positive values found for DeltaS(double dagger) and DeltaV(double dagger). The X-ray structure of the oxidized complex has been determined, and it is clearly indicative of the above-mentioned solvent-assisted hydrogen bonding between nitrogen and cyanide donors on the cobalt and iron centers, respectively. trans-[(LCoNCFeIII)-Co-14S-N-III(CN)(6)], as well as the analogous N-5 systems trans-[(LCoNCFeIII)-Co-14-N-III(CN)(6)], trans-[(LCoNCFeIII)-Co-15-N-III-(CN)(6)], and cis-[(LCoNCFeIII)-Co-n-N-III(CN)(6)], Oxidize water to hydrogen peroxide at pH > 10 with a rather simple stoichiometry, i.e., [(LCoNCFeIII)-Co-n-N-III(CN)(5)] + OH- - [(LCoNCFeII)-Co-n-N-III(CN)(5)](-) + 1/2H(2)O(2). In this way, the reversibility of the iron oxidation process is achieved. The determination of kinetic and thermal and pressure activation parameters for this water to hydrogen peroxide oxidation leads to the kinetic determination of a cyanide based OH- adduct of the complex. A second-order dependence on the base concentration is associated with deprotonation of this adduct to produce the final inner-sphere reduction process. The activation enthalpies are found to be extremely low (15 to 35 kJ mol(-1)) and responsible for the very fast reaction observed. The values of DeltaS(double dagger) and DeltaV(double dagger) (-76 to -113 J K-1 mol(-1) and -5.5 to -8.9 cm(3) mol(-1), respectively) indicate a highly organized but not very compressed transition state in agreement with the inner-sphere one-electron transfer from O2- to Fe-III.

Coral mortality increases wave energy reaching shores protected by reef flats: Examples from the Seychelles

In the granitic Seychelles, many shores and beaches are fringed by coral reef flats which provide protection to shores from erosion by waves. The surfaces of these reef flats support a complex ecology. About 10 years ago their seaward zones were extensively covered by a rich coral growth, which reached approximately to mean low water level, but in 1998 this was largely killed by seawater warming. The resulting large expanses of dead coral skeletons in these locations are now disintegrating, and much of the subsequent modest recovery by new coral recruitment was set back by further mortalities. A mathematical model of wave energy reaching shorelines protected by coral reef flats has been applied to 14 Seychelles reefs. It is derived from equations which predict: (1) the raised water level, or wave set-up, on reef flats resulting from wave breaking, which depends upon offshore wave height and period, depth of still water over the reef flat and the reef crest profile, and (2) the decay of energy from reef edge to shoreline that is affected by width of reef flat, surface roughness, sea level rise and 'pseudo-sea level rise' created by increased depth resulting from disintegration of coral colonies. The model treats each reef as one entity, but because biota and zonation on reef flats are not homogenous, all reefs are divided into four zones. In each, cover by both living and dead biota was estimated for calculation of parameters, and then averaged to obtain input data for the model. All possible biological factors were taken into account, such as the ability of seagrass beds to grow upwards to match expected sea level rise, reduction in height of the reef flat in relation to sea level as zones of dead corals decay, and the observed 'rounding' of reef crests as erosion removes corals from those areas. Estimates were also made of all these factors for a time approximately a decade ago, representing a time before the mass coral mortality, and for approximately a decade in the future when the observed rapid state of dead coral colony disintegration is assumed to have reached an end point. Results of increased energy over the past decade explain observations of erosion in some sites in the Seychelles. Most importantly, it is estimated that the rise in energy reaching shores protected by fringing reefs will now accelerate more rapidly, such that the increase expected over the next decade will be approximately double than that seen over the past decade. (c) 2005 Elsevier Ltd. All rights reserved.

Partitioning of deformation within a subduction channel during exhumation of high-pressure rocks: a case study from the Western Alps

The metamorphic belt of the Western Alps was subjected to widespread extensional tectonism at the end of the Eocene (ca. 45-35 Ma). Extension was accommodated by hinterland-directed movements along gently inclined extensional shear zones, which facilitated rapid exhumation of high-pressure and ultra-high-pressure rocks. This deformation resulted in a normal metamorphic sequence. Extension in the inner parts of the Western Alps was coeval with shortening at the front of the belt (foreland-directed thrusts), which took place during decompression, and emplaced higher grade metamorphic units over lower grade metamorphic rocks, thus forming an inverse metamorphic sequence. Two mechanisms for this extensional episode are discussed: (1) collapse of an overthickened lithosphere, and (2) internal readjustments within the orogenic wedge due to subduction channel dynamics. We favour the latter mechanism because it can account for the development of the observed inverse and normal metamorphic sequences along foreland-directed thrusts and hinterland-directed detachments, respectively. This hypothesis is supported by published structural, metamorphic and geochronological data from four geological transects through the Western Alps. This study also emphasizes the importance of post-shearing deformation (e.g. horizontal buckling versus vertical flattening), which can modify the distribution of hinterland- and foreland-directed shear zones in orogenic belts. (c) 2006 Elsevier Ltd. All rights reserved.

An investigation into children’s inductive reasoning strategies:What drives the development of category induction?

In a series of studies, I investigated the developmental changes in children’s inductive reasoning strategy, methodological manipulations affecting the trajectory, and driving mechanisms behind the development of category induction. I systematically controlled the nature of the stimuli used, and employed a triad paradigm in which perceptual cues were directly pitted against category membership, to explore under which circumstances children used perceptual or category induction. My induction tasks were designed for children aged 3-9 years old using biologically plausible novel items. In Study 1, I tested 264 children. Using a wide age range allowed me to systematically investigate the developmental trajectory of induction. I also created two degrees of perceptual distractor – high and low – and explored whether the degree of perceptual similarity between target and test items altered children’s strategy preference. A further 52 children were tested in Study 2, to examine whether children showing a perceptual-bias were in fact basing their choice on maturation categories. A gradual transition was observed from perceptual to category induction. However, this transition could not be due to the inability to inhibit high perceptual distractors as children of all ages were equally distracted. Children were also not basing their strategy choices on maturation categories. In Study 3, I investigated category structure (featural vs. relational category rules) and domain (natural vs. artefact) on inductive preference. I tested 403 children. Each child was assigned to either the featural or relational condition, and completed both a natural kind and an artefact task. A further 98 children were tested in Study 4, on the effect of using stimuli labels during the tasks. I observed the same gradual transition from perceptual to category induction preference in Studies 3 and 4. This pattern was stable across domains, but children developed a category-bias one year later for relational categories, arguably due to the greater demands on executive function (EF) posed by these stimuli. Children who received labels during the task made significantly more category choices than those who did not receive labels, possibly due to priming effects. Having investigated influences affecting the developmental trajectory, I continued by exploring the driving mechanism behind the development of category induction. In Study 5, I tested 60 children on a battery of EF tasks as well as my induction task. None of the EF tasks were able to predict inductive variance, therefore EF development is unlikely to be the driving factor behind the transition. Finally in Study 6, I divided 252 children into either a comparison group or an intervention group. The intervention group took part in an interactive educational session at Twycross Zoo about animal adaptations. Both groups took part in four induction tasks, two before and two a week after the zoo visits. There was a significant increase in the number of category choices made in the intervention condition after the zoo visit, a result not observed in the comparison condition. This highlights the role of knowledge in supporting the transition from perceptual to category induction. I suggest that EF development may support induction development, but the driving mechanism behind the transition is an accumulation of knowledge, and an appreciation for the importance of category membership.

Efficiency improvements to the Groupe Special Mobile (GSM) digital mobile radio system

Groupe Spécial Mobile (GSM) has been developed as the pan-European second generation of digital mobile systems. GSM operates in the 900 MHz frequency band and employs digital technology instead of the analogue technology of its predecessors. Digital technology enables the GSM system to operate in much smaller zones in comparison with the analogue systems. The GSM system will offer greater roaming facilities to its subscribers, extended throughout the countries that have installed the system. The GSM system could be seen as a further enhancement to European integration. GSM has adopted a contention-based protocol for multipoint-to-point transmission. In particular, the slotted-ALOHA medium access protocol is used to coordinate the transmission of the channel request messages between the scattered mobile stations. Collision still happens when more than one mobile station having the same random reference number attempts to transmit on the same time-slot. In this research, a modified version of this protocol has been developed in order to reduce the number of collisions and hence increase the random access channel throughput compared to the existing protocol. The performance evaluation of the protocol has been carried out using simulation methods. Due to the growing demand for mobile radio telephony as well as for data services, optimal usage of the scarce availability radio spectrum is becoming increasingly important. In this research, a protocol has been developed whereby the number of transmitted information packets over the GSM system is increased without any additional increase of the allocated radio spectrum. Simulation results are presented to show the improvements achieved by the proposed protocol. Cellular mobile radio networks commonly respond to an increase in the service demand by using smaller coverage areas. As a result, the volume of the signalling exchanges increases. In this research, a proposal for interconnecting the various entitles of the mobile radio network over the future broadband networks based on the IEEE 802.6 Metropolitan Area Network (MAN) is outlined. Simulation results are presented to show the benefits achieved by interconnecting these entities over the broadband Networks.

The reactions of carbon dioxide with complexes

The studies described in this thesis are concerned with the reaction of carbon dioxide and transition metal complexes of Co, Ir, Rh, Ru. Due to the important role of group VIII transition metals in homogeneous catalytic reactions, the work is mainly concerned with complexes of ruthenium.

Accessibility indices and linked trips: a case study of the elderly

The confusion over the concept of accessibility in transport planning and the deficiencies of existing accessibility indices are examined by developing a conceptual framework of accessibility with a fundamental distinction being drawn between the, often conflicting, theoretical and practical dimensions. The theoretical validity of alternative indices is assessed with reference to the problems and assumptions implicit in defining, measuring, valuing and aggregating the variables and components comprising accessibility. The major deficiencies of existing indices are identified as the inability of indices to take account of the potential to link trips between more than one activity location and the level of assumptions implicit in valuing and aggregating accessibility information. In this context, it is argued that accessibility information is more appropriately expressed on a comparative basis in the form of a profile rather than as a composite single-unit index and that the present confines of accessibility measurement must be extended in line with current developments in disaggregate travel and activity modelling. The sensitivity of accessibility levels to the use of alternative value judgements, alternative forms and levels of aggregation and the inclusion of information on the potential to link trips is examined by undertaking a case study. Accessibility profiles are developed for 23 zones in the London Borough of Hammersmith and Fulham showing the accessibility of the elderly to post offices and grocers. In a practical context, the profiles assist in identifying areas and individuals with relatively poor accessibility. The incidence and nature of linked trip-making and its significance and implications for accessibility measurement are explored further by analysing the results of a survey of the elderly's travel patterns. It is concluded that future accessibility analysis should be undertaken at a disaggregate level, taking account of the potential opportunity available from nonhome as well as home origins.

Novel pH‐and temperature‐responsive methacrylamide microgels

A novel transition temperature in MeAM copolymer microgels is reported. Despite the fact that MeAM homopolymers do not show thermosensitive properties, a specific synthetic strategy leads to a thermo-responsive swelling behavior that could be potentially useful in medical and/or industrial applications. The pH and temperature-dependent swelling response of microgels of MeAM copolymerized with 2-aminomethylpyridine and ethylenediamine is reported. The changes in particle sizes, which depend on the nature of the surrounding environment, are recorded by QELS. The relation between copolymer structure and its novel behavior is analyzed by several techniques (1H NMR, TGA).

High-visibility photonic crystal fiber interferometer as multifunctional sensor

A photonic crystal fiber (PCF) interferometer that exhibits record fringe contrast (~40 dB) is demonstrated along with its sensing applications. The device operates in reflection mode and consists of a centimeter-long segment of properly selected PCF fusion spliced to single mode optical fibers. Two identical collapsed zones in the PCF combined with its modal properties allow high-visibility interference patterns. The interferometer is suitable for refractometric and liquid level sensing. The measuring refractive index range goes from 1.33 to 1.43 and the maximum resolution is ~1.6 × 10-5. © 2013 by the authors; licensee MDPI, Basel, Switzerland.

Application of Two-Phase Regression to Geotechnical Data

2000 Mathematics Subject Classification: 62F10, 62J05, 62P30

The effect of the reproductivity's velocity on the biodiversity of a theoretical ecosystem

Climate change has a great impact on the build and the work of natural ecosystems. Disappearance of some population or growth of the number in some species can be already caused by little change in temperature. A Theoretical Ecosystem Growth Model was investigated in order to examine the effects of various climate patterns on the ecological equilibrium. This paper examines the diversity of a theoretical ecosystem on the grounds of changing in temperature-climate patterns. Simulations were made from the simplest case to the more complex exercise to explain harder questions. Daily temperature values were calculated according to various functions. The effect of existing climate patterns (historical or future daily temperatures) was analysed where temperature values were from various climatic zones. In this paper it is examined what kind of environmental conditions result larger diversity related to the velocity of reproduction.

Study of the physical properties of metals and oxides at extreme pressure and temperature conditions

The high-pressure and temperature investigations on transition metals, metal doped-oxide system, nanocrystalline materials are presented in this dissertation. The metal-doped oxide systems are technologically important because of their applications, e.g. LSC, opto electronic applications, luminescence from lasers, etc., and from the earth sciences point of view, e.g. the study of trace elements in the MgO-SiO2 system, which accounts for 50% of the Earth's chondritic model. We have carried out thorough investigations on Cr2O3 and on chromium bearing oxides at high PT-conditions using in situ X-ray diffractometry and florescence spectroscopy techniques. Having obtained exciting results, an attempt to focus on the mechanism of the coordination of transition metals in oxides has been made. Additionally, the florescence from the metals in host oxides was found to be helpful to obtain information on structural variations like changes in the coordination of the doped element, formation of new phases, the diffusion processes. The possible reactions taking place at extreme conditions in the MgO-SiO2 system has been observed using florescence as markers. A new heating assemblage has been designed and fabricated for a precise determination of temperature at high pressures. An equation combining pressure shifts of ruby wavelength and temperature has been proposed. We observed that the compressibility of nanocrystalline material (MgO and Ni) is independent of crystallite size. A reduction in the transition pressure of nanocrystalline ceria at high-pressure has been observed as compare to the corresponding bulk material. ^

The study of silicates and refractory materials at high pressures and temperatures

To better understand high pressure behavior of solids, both silicates and oxides have been investigated to clarify the high pressure melting, phase transformations and thermal parameters as well as their size dependences, both theoretically and experimentally. ^ To judge the precision of data determined experimentally, the reliabilities of different high pressure techniques have been discussed. A thermodynamic model has been developed and demonstrated to be able to closely reproduce the melting of solids by comparison between results calculated and data obtained experimentally, including metals (Al, Ni and Pt), Silicates (Mg3Al 2Si3O12 and CaMgSi2O6), Halides (NaCl, CsCl and LiF) and Oxides (MgO, FeO and Al2O3). The melting data obtained have been discussed to address the dynamics of the Earth's interior. ^ Results obtained with Raman spectroscopy and x-ray diffraction show that solids including silicates (andradite and pyrope) and oxides (CeO2 and TiO2) undergo a series of pressure-induced phase transformations. The effects of particle size under high pressures have been investigated. The results obtained indicate that the reduction of particle size leads to the enhancement of the bulk modulus and a significant decrease of transition pressure in TiO2 (rutile) and CeO2. The pressure-induced amorphization in anatase also results from the size effects. ^ Combining the data obtained with global seismic tomography, the physics and chemistry of the Earth's mantle and the dynamics of the core-mantle interaction have been discussed. The high pressure phases of Al3+- and Fe3+-bearing minerals play important roles in the dynamics of the lower mantle. ^

French Truffles and Forest Transitions

Truffle production in France has declined by more than 90% over the last 100 years. Commonly cited causes include a massive rural exodus that led to more open canopy forests becoming less intensively managed and reverting to closed canopy forests, the latter which do not favor truffle production. Scholars have labeled such a process as a forest transition, when a location goes from previously losing forest cover to regrowth and net gains in forest cover. Scholars have single out France as a place with a marked forest transition. Commonly these increases in forest cover are assumed to be a beneficial public good. Here, I question if it is accurate to view forest transitions as being universally beneficial, especially considering that this changing ecology has had strongly deleterious impacts on truffle production and those who rely on it for revenue. In this study I will use remote sensed images to examine if a forest transition did in fact occur in the department of Lot, France and what are the impacts forest trends have had on truffle cultivation. I will further estimates potential losses of revenue from truffle production which has resulted from any existing forest transition.