Compact Ag@fe3o4 Core-shell Nanoparticles By Means Of Single-step Thermal Decomposition Reaction.

A temperature pause introduced in a simple single-step thermal decomposition of iron, with the presence of silver seeds formed in the same reaction mixture, gives rise to novel compact heterostructures: brick-like Ag@Fe3O4 core-shell nanoparticles. This novel method is relatively easy to implement, and could contribute to overcome the challenge of obtaining a multifunctional heteroparticle in which a noble metal is surrounded by magnetite. Structural analyses of the samples show 4 nm silver nanoparticles wrapped within compact cubic external structures of Fe oxide, with curious rectangular shape. The magnetic properties indicate a near superparamagnetic like behavior with a weak hysteresis at room temperature. The value of the anisotropy involved makes these particles candidates to potential applications in nanomedicine.

Combining Legendre's Polynomials and Genetic Algorithm in the Solution of Nonlinear Initial-Value Problems

This work develops a method for solving ordinary differential equations, that is, initial-value problems, with solutions approximated by using Legendre's polynomials. An iterative procedure for the adjustment of the polynomial coefficients is developed, based on the genetic algorithm. This procedure is applied to several examples providing comparisons between its results and the best polynomial fitting when numerical solutions by the traditional Runge-Kutta or Adams methods are available. The resulting algorithm provides reliable solutions even if the numerical solutions are not available, that is, when the mass matrix is singular or the equation produces unstable running processes.

Singular Perturbation for the Discounted Continuous Control of Piecewise Deterministic Markov Processes

This paper deals with the expected discounted continuous control of piecewise deterministic Markov processes (PDMP`s) using a singular perturbation approach for dealing with rapidly oscillating parameters. The state space of the PDMP is written as the product of a finite set and a subset of the Euclidean space a""e (n) . The discrete part of the state, called the regime, characterizes the mode of operation of the physical system under consideration, and is supposed to have a fast (associated to a small parameter epsilon > 0) and a slow behavior. By using a similar approach as developed in Yin and Zhang (Continuous-Time Markov Chains and Applications: A Singular Perturbation Approach, Applications of Mathematics, vol. 37, Springer, New York, 1998, Chaps. 1 and 3) the idea in this paper is to reduce the number of regimes by considering an averaged model in which the regimes within the same class are aggregated through the quasi-stationary distribution so that the different states in this class are replaced by a single one. The main goal is to show that the value function of the control problem for the system driven by the perturbed Markov chain converges to the value function of this limit control problem as epsilon goes to zero. This convergence is obtained by, roughly speaking, showing that the infimum and supremum limits of the value functions satisfy two optimality inequalities as epsilon goes to zero. This enables us to show the result by invoking a uniqueness argument, without needing any kind of Lipschitz continuity condition.

Changes in the amount of soluble carbohydrates and polyphenols contents during decomposition of Montrichardia arborescens (L.) Schott

This study describes the aerobic and anaerobic decay of soluble carbohydrates (CH) and polyphenols (PH) during decomposition of Montrichardia arborescens. Plant and water samples were collected in the Cantá stream (2º 49' 11" N and 60º 40' 24" W), Roraima, Brazil. Decomposition chambers with plant fragments and stream water were incubated. Particulate organic matter was separated from dissolved organic matter and concentrations of CH and PH were determined. The results were fitted to 1st order kinetics models. CH and PH comprised a labile fraction (LCH and LPH) and a refractory fraction (RCH and RPH). The global coefficient associated with LCH weight loss was 1.4 times higher under aerobic conditions (3.4 day-1) higher than for anaerobic conditions. On the other hand, the RCH decay rate in the anaerobic process (0.0074 day-1) was 1.39 times higher. LCH was estimated to be 92% while RCH amounted to 8%. The LPH anaerobic decay was 5.2 times the value for the aerobic decay (0.67 day-1). For both conditions, RPH decay coefficients were similar (» 0.011 day-1). In the aerobic experiments LPH and RPH corresponded to 92.5% and 7.5%, respectively. For the anaerobic process these contents were 85.5% and 14.5%, respectively. From these results, we concluded that in the Cantá stream, the anaerobic degradation of phenols is more efficient than the aerobic counterpart. The aerobic condition provides a faster decay of carbohydrates of this plant.

Value and prices in Russian economic thought (1890-1920)

The subject "Value and prices in Russian economic thought (1890--1920)" should evoke several names and debates in the reader's mind. For a long time, Western scholars have been aware that the Russian economists Tugan-Baranovsky and Bortkiewicz were active participants to the Marxian transformation problem, that the mathematical models of Dmitriev prefigured forthcoming neoricardian based models, and that many Russian economists were either supporting the Marxian labour theory of value or being revisionists. Moreover, these ideas were preparing the ground for Soviet planning. Russian scholars additionally knew that this period was the time of introduction of marginalism in Russia, and that, during this period, economists were active in thinking the relation of ethics with economic theory. All these issues are well covered in the existing literature. But there is a big gap that this dissertation intends to fill. The existing literature handles these pieces separately, although they are part of a single, more general, history. All these issues (the labour theory of value, marginalism, the Marxian transformation problem, planning, ethics, mathematical economics) were part of what this dissertation calls here "The Russian synthesis". The Russian synthesis (in the singular) designates here all the attempts at synthesis between classical political economy and marginalism, between labour theory of value and marginal utility, and between value and prices that occurred in Russian economic thought between 1890 and 1920, and that embraces the whole set of issues evoked above. This dissertation has the ambition of being the first comprehensive history of that Russian synthesis. In this, this contribution is unique. It has always surprised the author of the present dissertation that such a book has not yet been written. Several good reasons, both in terms of scarce availability of sources and of ideological restrictions, may accounted for a reasonable delay of several decades. But it is now urgent to remedy the situation before the protagonists of the Russian synthesis are definitely classified under the wrong labels in the pantheon of economic thought. To accomplish this task, it has seldom be sufficient to gather together the various existing studies on aspects of this story. It as been necessary to return to the primary sources in the Russian language. The most important part of the primary literature has never been translated, and in the last years only some of them have been republished in Russian. Therefore, most translations from the Russian have been made by the author of the present dissertation. The secondary literature has been surveyed in the languages that are familiar (Russian, English and French) or almost familiar (German) to the present author, and which are hopefully the most pertinent to the present investigation. Besides, and in order to increase the acquaintance with the text, which was the objective of all this, some archival sources were used. The analysis consists of careful chronological studies of the authors' writings and their evolution in their historical and intellectual context. As a consequence, the dissertation brings new authors to the foreground - Shaposhnikov and Yurovsky - who were traditionally confined to the substitutes' bench, because they only superficially touched the domains quoted above. In the Russian synthesis however, they played an important part of the story. As a side effect, some authors that used to play in the foreground - Dmitriev and Bortkiewicz - are relegated to the background, but are not forgotten. Besides, the dissertation refreshes the views on authors already known, such as Ziber and, especially, Tugan-Baranovsky. The ultimate objective of this dissertation is to change the opinion that one could have on "value and prices in Russian economic thought", by setting the Russian synthesis at the centre of the debates.

Estimating the value of the metal-ligand bond dissociation enthalpy<D> (M-L) for adducts using empirical equations supported by TG data

In this work is presented and tested (for 106 adducts, mainly of the zinc group halides) two empirical equations supported in TG data to estimate the value of the metal-ligand bond dissociation enthalpy for adducts: <D> (M-O) = t i / g if t i < 420 K and <D> (M-O) = (t i / g ) - 7,75 . 10-2 . t i if t i > 420 K. In this empirical equations, t i is the thermodynamic temperature of the beginning of the thermal decomposition of the adduct, as determined by thermogravimetry, andg is a constant factor that is function of the metal halide considered and of the number of ligands, but is not dependant of the ligand itself. To half of the tested adducts the difference between experimental and calculated values was less than 5%. To about 80% of the tested adducts, the difference between the experimental (calorimetric) and the calculated (using the proposed equations) values are less than 15%.

Decomposition kinetics of gaseous ozone in peanuts

This study was conducted to evaluate the decomposition kinetics of gaseous ozone in peanut grains. This evaluation was made with 1-kg peanut samples, moisture contents being 7.1 and 10.5% wet basis (w.b.), placed in 3-liter glass containers. The peanut grains were ozonated at the concentration of 450 µg L-1, at 25 and 35 ºC, with gas flow rates of 1.0 and 3.0 L min-1. Time of saturation was determined by quantifying the residual concentration of ozone after the gas passed through the grains to constant mass. The decomposition kinetics of ozone was evaluated after the grain mass was ozone-saturated. For the peanut grains whose moisture content was 7.1% (w.b.), at 25 and 35ºC and with flow rates of 1.0 and 3.0 L min-1, the values obtained for time of saturation of gaseous ozone ranged between 173 and 192 min; the concentration of saturation was approximately 260 µg L-1. For the grains whose moisture content was 10.5% (w.b.), a higher residual concentration of gaseous ozone was obtained at 25 ºC, that of 190 µg L-1. As regards the half-life of ozone, the highest value obtained was equivalent to 7.7 min for grains ozonated at 25 ºC, while for those with moisture content of 10.5% at 35 ºC, half-life was 3.2 min. In the process of ozone decomposition in peanut grains, temperature was concluded to be the key factor. An increase of 10 ºC in the temperature of the grains results in a decrease of at least 43% in the half-life of ozone.

Theory of differential inequalities with appliciations to singular perturbiation problems and method of lines

During recent years, the theory of differential inequalities has been extensively used to discuss singular perturbation problems and method of lines to partial differential equations. The present thesis deals with some differential inequality theorems and their applications to singularly perturbed initial value problems, boundary value problems for ordinary differential equations in Banach space and initial boundary value problems for parabolic differential equations. The method of lines to parabolic and elliptic differential equations are also dealt The thesis is organised into nine chapters

Nichtüberlappende Gebietszerlegungsmethoden für lineare und quasilineare (monotone und nichtmonotone) Probleme

In dieser Arbeit werden nichtüberlappende Gebietszerlegungsmethoden einerseits hinsichtlich der zu lösenden Problemklassen verallgemeinert und andererseits in bisher nicht untersuchten Kontexten betrachtet. Dabei stehen funktionalanalytische Untersuchungen zur Wohldefiniertheit, eindeutigen Lösbarkeit und Konvergenz im Vordergrund. Im ersten Teil werden lineare elliptische Dirichlet-Randwertprobleme behandelt, wobei neben Problemen mit dominantem Hauptteil auch solche mit singulärer Störung desselben, wie konvektions- oder reaktionsdominante Probleme zugelassen sind. Der zweite Teil befasst sich mit (gleichmäßig) monotonen koerziven quasilinearen elliptischen Dirichlet-Randwertproblemen. In beiden Fällen wird das Lipschitz-Gebiet in endlich viele Lipschitz-Teilgebiete zerlegt, wobei insbesondere Kreuzungspunkte und Teilgebiete ohne Außenrand zugelassen sind. Anschließend werden Transmissionsprobleme mit frei wählbaren $L^{\infty}$-Parameterfunktionen hergeleitet, wobei die Konormalenableitungen als Funktionale auf geeigneten Funktionenräumen über den Teilrändern ($H_{00}^{1/2}(\Gamma)$) interpretiert werden. Die iterative Lösung dieser Transmissionsprobleme mit einem Ansatz von Deng führt auf eine Substrukturierungsmethode mit Robin-artigen Transmissionsbedingungen, bei der eine Auswertung der Konormalenableitungen aufgrund einer geschickten Aufdatierung der Robin-Daten nicht notwendig ist (insbesondere ist die bekannte Robin-Robin-Methode von Lions als Spezialfall enthalten). Die Konvergenz bezüglich einer partitionierten $H^1$-Norm wird für beide Problemklassen gezeigt. Dabei werden keine über $H^1$ hinausgehende Regularitätsforderungen an die Lösungen gestellt und die Gebiete müssen keine zusätzlichen Glattheitsvoraussetzungen erfüllen. Im letzten Kapitel werden nichtmonotone koerzive quasilineare Probleme untersucht, wobei das Zugrunde liegende Gebiet nur in zwei Lipschitz-Teilgebiete zerlegt sein soll. Das zugehörige nichtlineare Transmissionsproblem wird durch Kirchhoff-Transformation in lineare Teilprobleme mit nichtlinearen Kopplungsbedingungen überführt. Ein optimierungsbasierter Lösungsansatz, welcher einen geeigneten Abstand der rücktransformierten Dirichlet-Daten der linearen Teilprobleme auf den Teilrändern minimiert, führt auf ein optimales Kontrollproblem. Die dabei entstehenden regularisierten freien Minimierungsprobleme werden mit Hilfe eines Gradientenverfahrens unter minimalen Glattheitsforderungen an die Nichtlinearitäten gelöst. Unter zusätzlichen Glattheitsvoraussetzungen an die Nichtlinearitäten und weiteren technischen Voraussetzungen an die Lösung des quasilinearen Ausgangsproblems, kann zudem die quadratische Konvergenz des Newton-Verfahrens gesichert werden.

An interpretation of baroclinic initial value problems: results for simple basic states with nonzero interior PV gradients

In the Eady model, where the meridional potential vorticity (PV) gradient is zero, perturbation energy growth can be partitioned cleanly into three mechanisms: (i) shear instability, (ii) resonance, and (iii) the Orr mechanism. Shear instability involves two-way interaction between Rossby edge waves on the ground and lid, resonance occurs as interior PV anomalies excite the edge waves, and the Orr mechanism involves only interior PV anomalies. These mechanisms have distinct implications for the structural and temporal linear evolution of perturbations. Here, a new framework is developed in which the same mechanisms can be distinguished for growth on basic states with nonzero interior PV gradients. It is further shown that the evolution from quite general initial conditions can be accurately described (peak error in perturbation total energy typically less than 10%) by a reduced system that involves only three Rossby wave components. Two of these are counterpropagating Rossby waves—that is, generalizations of the Rossby edge waves when the interior PV gradient is nonzero—whereas the other component depends on the structure of the initial condition and its PV is advected passively with the shear flow. In the cases considered, the three-component model outperforms approximate solutions based on truncating a modal or singular vector basis.

The impact of two arable field margin management schemes on litter decomposition

A primary objective of agri-environment schemes is the conservation of biodiversity; in addition to increasing the value of farmland for wildlife, these schemes also aim to restore natural ecosystem functioning. The management of scheme options can influence their value for delivering ecosystem services by modifying the composition of floral and faunal communities. This study examines the impact of an agri-environment scheme prescription on ecosystem functioning by testing the hypothesis that vegetation management influences decomposition rates in grassy arable field margins. The effects of two vegetation management practices in arable field margins - cutting and soil disturbance (scarification) - on litter decomposition were compared using a litterbag experimental approach in early April 2006. Bags had either small mesh designed to restrict access to soil macrofauna, or large mesh that would allow macrofauna to enter. Bags were positioned on the soil surface or inserted into the soil in cut and scarified margins, retrieved after 44, 103 and 250 days and the amount of litter mass remaining was calculated. Litter loss from the litterbags with large mesh was greater than from the small mesh bags, providing evidence that soil macrofauna accelerate rates of litter decomposition. In the large mesh bags, the proportion of litter remaining in bags above and belowground in the cut plots was similar, while in the scarified plots, there was significantly more litter left in the aboveground bags than in the belowground bags. This loss of balance between decomposition rates above and belowground in scarified margins may have implications for the development and maintenance of grassy arable field margins by influencing nutrient availability for plant communities. (C) 2008 Elsevier B.V. All rights reserved.

Higher oxides of chlorine: absorption cross-sections of Cl2O6 and Cl2O4, the decomposition of Cl2O6, and the reactions of OClO with O and O-3

The absorption cross-sections of Cl2O6 and Cl2O4 have been obtained using a fast flow reactor with a diode array spectrometer (DAS) detection system. The absorption cross-sections at the wavelengths of maximum absorption (lambda(max)) determined in this study are those of Cl2O6: (1.47 +/- 0.15) x 10(-17) cm(2) molecule(-1), at lambda(max) = 276 nm and T = 298 K; and Cl2O4: (9.0 +/- 2.0) x 10(-19) cm(2) molecule(-1), at lambda(max) = 234 nm and T = 298 K. Errors quoted are two standard deviations together with estimates of the systematic error. The shapes of the absorption spectra were obtained over the wavelength range 200-450 nm for Cl2O6 and 200-350 nm for Cl2O4, and were normalized to the absolute cross-sections obtained at lambda(max) for each oxide, and are presented at 1 nm intervals. These data are discussed in relation to previous measurements. The reaction of O with OCIO has been investigated with the objective of observing transient spectroscopic absorptions. A transient absorption was seen, and the possibility is explored of identifying the species with the elusive sym-ClO3 or ClO4, both of which have been characterized in matrices, but not in the gas-phase. The photolysis of OCIO was also re-examined, with emphasis being placed on the products of reaction. UV absorptions attributable to one of the isomers of the ClO dimer, chloryl chloride (ClClO2) were observed; some Cl2O4 was also found at long photolysis times, when much of the ClClO2 had itself been photolysed. We suggest that reports of Cl2O6 formation in previous studies could be a consequence of a mistaken identification. At low temperatures, the photolysis of OCIO leads to the formation of Cl2O3 as a result of the addition of the ClO primary product to OCIO. ClClO2 also appears to be one product of the reaction between O-3 and OCIO, especially when the reaction occurs under explosive conditions. We studied the kinetics of the non-explosive process using a stopped-flow technique, and suggest a value for the room-temperature rate coefficient of (4.6 +/- 0.9) x 10(-19) cm(3) molecule(-1) s(-1) (limit quoted is 2sigma random errors). The photochemical and thermal decomposition of Cl2O6 is described in this paper. For photolysis at k = 254 nm, the removal of Cl2O6 is not accompanied by the build up of any other strong absorber. The implications of the results are either that the photolysis of Cl2O6 produces Cl-2 directly, or that the initial photofragments are converted rapidly to Cl-2. In the thermal decomposition of Cl2O6, Cl2O4 was shown to be a product of reaction, although not necessarily the major one. The kinetics of decomposition were investigated using the stopped-flow technique. At relatively high [OCIO] present in the system, the decay kinetics obeyed a first-order law, with a limiting first-order rate coefficient of 0.002 s(-1). (C) 2004 Elsevier B.V. All rights reserved.

The kinetics of the gas-phase decomposition of the 2-methyl-2-butoxyl and 2-methyl-2-pentoxyl radicals

The kinetics of the title reactions have been studied by relative-rate methods as a function of temperature. Relative-rate coefficients for the two decomposition channels of 2-methyl-2-butoxyl have been measured at five different temperatures between 283 and 345 K and the observed temperature dependence is consistent with the results of some previous experimental studies. The kinetics of the two decomposition channels of 2-methyl-2-pentoxyl have also been investigated, as a function of temperature, relative to the estimated rate of isomerisation of this radical. Room-temperature rate coefficient data for the two decomposition channels of both 2-methyl-2-pentoxyl and 2-methyl-2-butxoyl (after combining the relative rate coefficient for this latter with a value for the rate coefficient of the major channel, extrapolated from the data presented by Batt et al., Int. J. Chem. Kinet., 1978, 10, 931) are shown to be consistent with a non-linear kinetic correlation, for alkoxyl radical decomposition rate data, previously presented by this laboratory (Johnson et al., Atmos. Environ., 2004, 38, 1755-1765).

On the numerical integration of a class of singular perturbation problems

A three-point difference scheme recently proposed in Ref. 1 for the numerical solution of a class of linear, singularly perturbed, two-point boundary-value problems is investigated. The scheme is derived from a first-order approximation to the original problem with a small deviating argument. It is shown here that, in the limit, as the deviating argument tends to zero, the difference scheme converges to a one-sided approximation to the original singularly perturbed equation in conservation form. The limiting scheme is shown to be stable on any uniform grid. Therefore, no advantage arises from using the deviating argument, and the most accurate and efficient results are obtained with the deviation at its zero limit.

Estimating reliability and resolution of probability forecasts through decomposition of the empirical score

References (20)Cited By (1)Export CitationAboutAbstract Proper scoring rules provide a useful means to evaluate probabilistic forecasts. Independent from scoring rules, it has been argued that reliability and resolution are desirable forecast attributes. The mathematical expectation value of the score allows for a decomposition into reliability and resolution related terms, demonstrating a relationship between scoring rules and reliability/resolution. A similar decomposition holds for the empirical (i.e. sample average) score over an archive of forecast–observation pairs. This empirical decomposition though provides a too optimistic estimate of the potential score (i.e. the optimum score which could be obtained through recalibration), showing that a forecast assessment based solely on the empirical resolution and reliability terms will be misleading. The differences between the theoretical and empirical decomposition are investigated, and specific recommendations are given how to obtain better estimators of reliability and resolution in the case of the Brier and Ignorance scoring rule.