One- and two-step spin-crossover behavior of [Fe(II)(isoxazole)6]2+ and the structure and magnetic properties of triangular [Fe(III)3O(OAc)6(isoxazole)3][ClO4)]

The structure and spin-crossover magnetic behavior of [FeII16][BF4]2 (1 = isoxazole) and [FeII16][ClO4]2 have been studied. [FeII16][BF4]2 undergoes two reversible spin-crossover transitions at 91 and 192 K, and is the first two-step spin transition to undergo a simultaneous crystallographic phase transition, but does not exhibit thermal hysteresis. The single-crystal structure determinations at 260 [space group P3̄, a = 17.4387(4) Å, c = 7.6847(2) Å] and at 130 K [space group P1̄, a = 17.0901(2) Å, b = 16.7481(2) Å, c = 7.5413(1) Å, α = 90.5309(6)°, β = 91.5231(6)°, γ = 117.8195(8)°] reveal two different iron sites, Fe1 and Fe2, in a 1:2 ratio. The room-temperature magnetic moment of 5.0 μB is consistent with high-spin Fe(II). A plateau in μ(T) having a moment of 3.3 μB centered at 130 K suggests a mixed spin system of some high-spin and some low-spin Fe(II) molecules. On the basis of the Fe−N bond distances at the two temperatures, and the molar fraction of high-spin molecules at the transition plateau, Fe1 and Fe2 can be assigned to the 91 and 192 K transitions, respectively. [FeII16][ClO4]2 [space group P3̄, a = 17.5829(3) Å, c = 7.8043(2) Å, β = 109.820 (3)°, T = 295 K] also possesses Fe1:Fe2 in a 1:2 ratio, and magnetic measurements show a single spin transition at 213 K, indicating that both Fe1 and Fe2 undergo a simultaneous spin transition. [FeII16][ClO4]2 slowly decomposes in solutions containing acetic anhydride to form [FeIII3O(OAc)613][ClO4] [space group I2, a = 10.1547(7) Å, b = 16.5497(11) Å, c = 10.3205(9) Å, β = 109.820 (3)°, T = 200 K]. The isosceles Fe3 unit contains two Fe···Fe distances of 3.2844(1) Å and a third Fe···Fe distance of 3.2857(1) Å. The magnetic data can be fit to a trinuclear model with ℋ = −2J(S1·S2 + S2·S3) − 2J13(S1·S3), where J = −27.1 and J13 = −32.5 cm-1.

Optimization of the Investment Portfolio in the Conditions of Uncertainty

Portfolio analysis exists, perhaps, as long, as people think about acceptance of rational decisions connected with use of the limited resources. However the occurrence moment of portfolio analysis can be dated precisely enough is having connected it with a publication of pioneer work of Harry Markovittz (Markovitz H. Portfolio Selection) in 1952. The model offered in this work, simple enough in essence, has allowed catching the basic features of the financial market, from the point of view of the investor, and has supplied the last with the tool for development of rational investment decisions. The central problem in Markovitz theory is the portfolio choice that is a set of operations. Thus in estimation, both separate operations and their portfolios two major factors are considered: profitableness and risk of operations and their portfolios. The risk thus receives a quantitative estimation. The account of mutual correlation dependences between profitablenesses of operations appears the essential moment in the theory. This account allows making effective diversification of portfolio, leading to essential decrease in risk of a portfolio in comparison with risk of the operations included in it. At last, the quantitative characteristic of the basic investment characteristics allows defining and solving a problem of a choice of an optimum portfolio in the form of a problem of quadratic optimization.

Branching Populations of Cells Bearing a Continuous Label

2000 Mathematics Subject Classification: 60J80.

Computer program for the analysis of non-prismatic beams

One of the major problems in the analysis of beams with Moment of Inertia varying along their length, is to find the Fixed End Moments, Stiffness, and Carry-Over Factors. In order to determine Fixed End Moments, it is necessary to consider the non-prismatic member as integrated by a large number of small sections with constant Moment of Inertia, and to find the M/EI values for each individual section. This process takes a lot of time from Designers and Structural Engineers. The object of this thesis is to design a computer program to simplify this repetitive process, obtaining rapidly and effectively the Final Moments and Shears in continuous non-prismatic Beams. For this purpose the Column Analogy and the Moment Distribution Methods of Professor Hardy Cross have been utilized as the principles toward the methodical computer solutions. The program has been specifically designed to analyze continuous beams of a maximum of four spans of any length, integrated by symmetrical members with rectangular cross sections and with rectilinear variation of the Moment of Inertia. Any load or combination of uniform and concentrated loads must be considered. Finally sample problems will be solved with the new Computer Program and with traditional systems, to determine the accuracy and applicability of the Program.

The international legal thought of Carl Schmitt : towards a critique of the contemporary international order

The aim of the thesis is to develop a critique of current liberal conceptualizations of international order. In order to conduct this critique, this thesis revisits the arguments first put forth by the German legal and political theorist Carl Schmitt. Schmitt conceptualizes a tripartite unity between law, order, and place. This unity, established at the constituent moment of land-appropriation, forms a concrete nomos, which subsequently creates the contours of the legal and political order. The establishment of the concrete order is necessarily the construction of a territorial boundary that designates an inside and an outside of the polity. By speaking of a nomos of the earth, Schmitt globalized this understanding of concrete order by looking at the various historical developments that created a "line" between the concrete applicability of interstate norms and a region where the exceptional situation prevails. The critique presented in this thesis is concerned with the lack of concrete boundary conditions within the current international legal order. It is argued that this lack of a well-defined boundary condition is what results in extreme forms of violence that were traditionally bracketed.

Impact on quality of life of removable partial denture wearers after 2 years of use

The use of clinical indicators of satisfaction (OHIP) can be applied to evaluate the impact of denture use on patient quality of life, since dental problems and disorders interfere in the normal life of individuals. Aim: This study aimed at evaluating the satisfaction level of patients rehabilitated with removable partial dentures (RPD) after 2 years of use. Methods: An observational study was carried out on 28 patients with a mean age of 45 years, treated with RPD at the Department of Dentistry of the Federal University of Rio Grande do Norte in 2005. Patients signed informed consent and answered the Oral Health Impact Profile (OHIP) questionnaire on three occasions: prior to rehabilitation and at 3 months and 2 years of denture use. Repeated-measures ANOVA was applied for data analysis. Results: A difference was found between data obtained at the moment of fitting and three months after denture use (p<0.001). However, no variation was observed when comparing data from 3 months and 2 years of use (p>0.05). The variables of gender and age did not interfere in the result (p>0.05). Conclusions: The degree of patient satisfaction after RPD installation was significant at the moment of fitting and 3 months after denture use, but no significant difference was found between 3 months and 2 years of denture use.

Impact on quality of life of removable partial denture wearers after 2 years of use

The use of clinical indicators of satisfaction (OHIP) can be applied to evaluate the impact of denture use on patient quality of life, since dental problems and disorders interfere in the normal life of individuals. Aim: This study aimed at evaluating the satisfaction level of patients rehabilitated with removable partial dentures (RPD) after 2 years of use. Methods: An observational study was carried out on 28 patients with a mean age of 45 years, treated with RPD at the Department of Dentistry of the Federal University of Rio Grande do Norte in 2005. Patients signed informed consent and answered the Oral Health Impact Profile (OHIP) questionnaire on three occasions: prior to rehabilitation and at 3 months and 2 years of denture use. Repeated-measures ANOVA was applied for data analysis. Results: A difference was found between data obtained at the moment of fitting and three months after denture use (p<0.001). However, no variation was observed when comparing data from 3 months and 2 years of use (p>0.05). The variables of gender and age did not interfere in the result (p>0.05). Conclusions: The degree of patient satisfaction after RPD installation was significant at the moment of fitting and 3 months after denture use, but no significant difference was found between 3 months and 2 years of denture use.

Introduction: resilience and the Anthropocene: the stakes of ‘renaturalising’ politics

The Anthropocene marks a new geological epoch in which human activity (and specifically Western production and consumption practices) has become a geological force. It also profoundly destabilizes the grounds of Western political philosophy. Visions of a dynamic earth system wholly indifferent to human survival liquefy modernity’s division between nature and politics. Critical thought has only begun to scratch the surface of the Anthropocene’s re-naturalization of politics. This special issue of Resilience: International Policies, Practices and Discourses explores the politics of resilience within the wider cultural and political moment of the Anthropocene. It is within the field of resilience thinking that the implications of the Anthropocene for forms of governance are beginning to be sketched out and experimental practices are undertaken. Foregrounding the Anthropocene imaginary’s re-naturalization of politics enables us to consider the political possibilities of resilience from a different angle, one that is irreducible to neoliberal post-political rule.

Projected equations of motion approach to hybrid quantum/classical dynamics in dielectric-metal composites

We introduce a hybrid method for dielectric-metal composites that describes the dynamics of the metallic system classically whilst retaining a quantum description of the dielectric. The time-dependent dipole moment of the classical system is mimicked by the introduction of projected equations of motion (PEOM) and the coupling between the two systems is achieved through an effective dipole-dipole interaction. To benchmark this method, we model a test system (semiconducting quantum dot-metal nanoparticle hybrid). We begin by examining the energy absorption rate, showing agreement between the PEOM method and the analytical rotating wave approximation (RWA) solution. We then investigate population inversion and show that the PEOM method provides an accurate model for the interaction under ultrashort pulse excitation where the traditional RWA breaks down.

First-Principles Study of the Electronic and Magnetic Properties of Defects in Carbon Nanostructures

Understanding the magnetic properties of graphenic nanostructures is instrumental in future spintronics applications. These magnetic properties are known to depend crucially on the presence of defects. Here we review our recent theoretical studies using density functional calculations on two types of defects in carbon nanostructures: Substitutional doping with transition metals, and sp$^3$-type defects created by covalent functionalization with organic and inorganic molecules. We focus on such defects because they can be used to create and control magnetism in graphene-based materials. Our main results are summarized as follows: i)Substitutional metal impurities are fully understood using a model based on the hybridization between the $d$ states of the metal atom and the defect levels associated with an unreconstructed D$_{3h}$ carbon vacancy. We identify three different regimes, associated with the occupation of distinct hybridization levels, which determine the magnetic properties obtained with this type of doping; ii) A spin moment of 1.0 $\mu_B$ is always induced by chemical functionalization when a molecule chemisorbs on a graphene layer via a single C-C (or other weakly polar) covalent bond. The magnetic coupling between adsorbates shows a key dependence on the sublattice adsorption site. This effect is similar to that of H adsorption, however, with universal character; iii) The spin moment of substitutional metal impurities can be controlled using strain. In particular, we show that although Ni substitutionals are non-magnetic in flat and unstrained graphene, the magnetism of these defects can be activated by applying either uniaxial strain or curvature to the graphene layer. All these results provide key information about formation and control of defect-induced magnetism in graphene and related materials.

Interplay of Defects, Magnetism, Ripples and Strain in Graphene

We present a comprehensive study based on first-principles calculations about the interplay of four important ingredients on the electronic structure of graphene: defects + magnetism + ripples + strain. So far they have not been taken into account simultaneously in a set of ab initio calculations. Furthermore, we focus on the strain dependence of the properties of carbon monovacancies, with special attention to magnetic spin moments. We demonstrated that such defects show a very rich structural and spin phase-diagram with many spin solutions as function of strain. At zero strain the vacancy shows a spin moment of 1.5 Bohrs that increases up to 2 Bohrs with stretching. Changes are more dramatic under compression: the vacancy becomes non-magnetic under a compression larger than 2%. This transition is linked to the structural modifications associated with the formation of ripples in the graphene layer. Our results suggest that such interplay could have important implications for the design of future spintronics devices based on graphene derivatives, as for example a spin-strain switch based on vacancies.

Sesamoids of the metatarsophalangeal joint of the big toe: a sistematic review

Abstract: The first metatarsal sesamoid bones are not always taken into consideration when making a diagnosis, in pathologies that affect the region of the first metatarsal head. This is due to the insufficient knowledge of all the pathologies that can affect the sesamoids and the relative little incidence that they have. With the increment of sports activities, in particular the running, increasingly affects of the symptoms concerning this region are observed. Methods: A literature search was performed in 5 databases (Medline, PubMed, Scopus, Cochrane Library and BUCEA). The terms included in the search were: sesamoids, anatomy, biomechanics, sesamoids review and sesamoids pathology. In the initial search articles with no more than 10 years, only humans and revision texts are considered. Results: 24 articles were selected and include different pathologies with diagnosis using imaging tests and treatments, both conservative and surgical; as well as aspects from the biomechanics of the metatarsal-sesamoid joint. Conclusion: Sesamoids due of his anatomy, topography and function can be involved in a lot of pathologies; with similar signs and symptoms that can confuse the podiatry when he has to make a correct diagnosis or treatment.

Revising Devotion: the role of wooden sculptures in affecting painting and devotion in the Late Medieval period in Italy (XII-XV century)

Thesis (Ph.D.)--University of Washington, 2016-06

Problems of optimal transportation on the circle and their mechanical applications

We consider a mechanical problem concerning a 2D axisymmetric body moving forward on the plane and making slow turns of fixed magnitude about its axis of symmetry. The body moves through a medium of non-interacting particles at rest, and collisions of particles with the body's boundary are perfectly elastic (billiard-like). The body has a blunt nose: a line segment orthogonal to the symmetry axis. It is required to make small cavities with special shape on the nose so as to minimize its aerodynamic resistance. This problem of optimizing the shape of the cavities amounts to a special case of the optimal mass transfer problem on the circle with the transportation cost being the squared Euclidean distance. We find the exact solution for this problem when the amplitude of rotation is smaller than a fixed critical value, and give a numerical solution otherwise. As a by-product, we get explicit description of the solution for a class of optimal transfer problems on the circle.

Moments of Rupture: Narratological Readings of Contemporary German Literature

Thesis (Ph.D.)--University of Washington, 2016-08