A química newtoniana

The work of Newton exerted a profound influence on the development of science. In chemistry this newtonian influence was present in Query 31 of Newton's Optics. However, the incursion of Newton's thought into chemistry brought upon the chemists an epistemological question, that of the nature of their discipline. Would chemistry be a discipline in its own right, or simply a branch of physics? In this work we present the newtonian program for chemistry, as well as the reaction of traditional chemists to it. We conclude by proposing that Lavoisier carried through a synthesis between newtonian methodology and the singularity of traditional chemistry.

Splat-based surface reconstruction from defect-laden point sets

We introduce a method for surface reconstruction from point sets that is able to cope with noise and outliers. First, a splat-based representation is computed from the point set. A robust local 3D RANSAC-based procedure is used to filter the point set for outliers, then a local jet surface - a low-degree surface approximation - is fitted to the inliers. Second, we extract the reconstructed surface in the form of a surface triangle mesh through Delaunay refinement. The Delaunay refinement meshing approach requires computing intersections between line segment queries and the surface to be meshed. In the present case, intersection queries are solved from the set of splats through a 1D RANSAC procedure

Propriedades estruturais e microestruturais de manganitas dopadas com cobre

We report a structural study on polycrystalline La0.86Sr0.14Mn1-y Cu yO3+delta samples (y = 0, 0.05, 0.10, 0.15, 0.20) using refinement of powder X-ray diffraction data and analysis of scanning electron microscopy images. It is found that the structure remains rhombohedral through the whole series, with a decrease in the average Mn-Mn bond distances, slight variations in Mn-O-Mn angle and reduction in the unit cell volume with increasing Cu amounts. The values of Mn-Mn distances suggest compact structures with d within ±1%. Scanning electron microscopy images reveal homogeneous microstructure in all samples, besides a trend for smaller grains and larger porosity with increasing Cu content.

Síntese hidrotermal assistida por micro-ondas como metodologia sintética eficiente para obtenção da rede metalorgânica [ZN(BDC)(H2O)2]n

This work presents the optimization of the microwave-assisted hydrothermal synthesis of [Zn(BDC)(H2O)2]n . The reactions were carried out at the fixed temperature of 120 ºC for 10, 20, 30 and 40 min. Pure crystalline [Zn(BDC)(H2O)2]n was obtained in high yield (ca. 90%) with a reaction time of 10 min. The phase obtained and its purity was confirmed by Rietveld refinement, with a final value for Rwp/Rexp equal to 1.48. Increased reaction times (20, 30 and 40 min) favored the formation of unwanted by products, resulting in mixtures of several crystalline phases.

Comparação estrutural entre amostras de materiais tipo hidrotalcita obtidas a partir de diferentes rotas de síntese

Three samples of hydrotalcite-like materials (HTC) were synthesized and their structural characteristics were compared with two HTCs obtained commercially. Thermal analyses, FT-IR, PXRD and textural analyses were used to investigate the structural differences between commercial and synthetic samples. Particularly, the memory effect was observed at temperature higher than 600 ºC. The Rietveld refinements were obtained with expressive accuracy and the statistical parameters of goodness of fit are quite satisfactory. In conclusion, the procedures adopted in synthesis of HTC produced crystalline materials with high surface area materials.

A regra de Bent contextualiza a força da ligação de hidrogênio em clusters trimoleculares

This article presents a theoretical study of the molecular properties of trimolecular clusters of CnHm∙∙∙HCN∙∙∙HX formed by the ϖ∙∙∙H and n∙∙∙H hydrogen bonds. The interaction strengths of these interactions are in line with the variations in s-character, and independently, the red-shift rise whether stronger or weaker bound systems are carried out. This behavior was justified via NBO analysis and supported by Bent´s rule, wherein the greater variations in s-character of X are in good agreement with larger red-shifts and vice-versa. To conclude, the refinement of the supermolecule approach and NBO binding energies also corroborate in this regard.

ATRIBUIÇÃO DA ESTEREOQUÍMICA DA α-SANTONINA ATRAVÉS DAS MEDIDAS DO ACOPLAMENTO DIPOLAR RESIDUAL

The measurement of nuclear magnetic resonance parameters in an anisotropic media, such as residual dipolar coupling (RDC), has proven to be an excellent methodology for the refinement of chemical structures, being used as a complementary tool in the determination of the relative configuration, conformation, and constitution of organic compounds. In this study, we applied this methodology to determine the relative configuration of α-santonin, a natural product with four stereocenters, while assigning its prochiral methylene protons using only the RDCs obtained in a polyacrylonitrile polymer gel swollen in DMSO-d6.

CFD Simulation of Two-phase and Three-phase Flows in Internal-loop Airlift

Airlift reactors are pneumatically agitated reactors that have been widely used in chemical, petrochemical, and bioprocess industries, such as fermentation and wastewater treatment. Computational Fluid Dynamics (CFD) has become more popular approach for design, scale-up and performance evaluation of such reactors. In the present work numerical simulations for internal-loop airlift reactors were performed using the transient Eulerian model with CFD package, ANSYS Fluent 12.1. The turbulence in the liquid phase is described using κ- ε the model. Global hydrodynamic parameters like gas holdup, gas velocity and liquid velocity have been investigated for a range of superficial gas velocities, both with 2D and 3D simulations. Moreover, the study of geometry and scale influence on the reactor have been considered. The results suggest that both, geometry and scale have significant effects on the hydrodynamic parameters, which may have substantial effects on the reactor performance. Grid refinement and time-step size effect have been discussed. Numerical calculations with gas-liquid-solid three-phase flow system have been carried out to investigate the effect of solid loading, solid particle size and solid density on the hydrodynamic characteristics of internal loop airlift reactor with different superficial gas velocities. It was observed that averaged gas holdup is significantly decreased with increasing slurry concentration. Simulations show that the riser gas holdup decreases with increase in solid particle diameter. In addition, it was found that the averaged solid holdup increases in the riser section with the increase of solid density. These produced results reveal that CFD have excellent potential to simulate two-phase and three-phase flow system.

Numerical Investigation of Flow Past a Circular Cylinder and in a Staggered Tube Bundle Using Various Turbulence Models

Transitional flow past a three-dimensional circular cylinder is a widely studied phenomenon since this problem is of interest with respect to many technical applications. In the present work, the numerical simulation of flow past a circular cylinder, performed by using a commercial CFD code (ANSYS Fluent 12.1) with large eddy simulation (LES) and RANS (κ - ε and Shear-Stress Transport (SST) κ - ω! model) approaches. The turbulent flow for ReD = 1000 & 3900 is simulated to investigate the force coefficient, Strouhal number, flow separation angle, pressure distribution on cylinder and the complex three dimensional vortex shedding of the cylinder wake region. The numerical results extracted from these simulations have good agreement with the experimental data (Zdravkovich, 1997). Moreover, grid refinement and time-step influence have been examined. Numerical calculations of turbulent cross-flow in a staggered tube bundle continues to attract interest due to its importance in the engineering application as well as the fact that this complex flow represents a challenging problem for CFD. In the present work a time dependent simulation using κ – ε, κ - ω! and SST models are performed in two dimensional for a subcritical flow through a staggered tube bundle. The predicted turbulence statistics (mean and r.m.s velocities) have good agreement with the experimental data (S. Balabani, 1996). Turbulent quantities such as turbulent kinetic energy and dissipation rate are predicted using RANS models and compared with each other. The sensitivity of grid and time-step size have been analyzed. Model constants sensitivity study have been carried out by adopting κ – ε model. It has been observed that model constants are very sensitive to turbulence statistics and turbulent quantities.

Romanssien ja runouden aikakausi. Thomas Warton keskiaikaa määrittelemässä 1750–1790

Tutkimukseni käsittelee keskiajan nousua historian tärkeäksi periodiksi 1700-luvun Englannissa näkökulmanaan Thomas Wartonin (1726–1790) kirjoitukset. Warton oli Oxfordin yliopistossa toiminut oppinut antikvaari. Wartonin pääteos History of English Poetry (1774–1781) ei nimestään huolimatta ollut moderni kirjallisuushistoria vaan 1000–1500-luvun kirjoitettua kulttuuria laajasti käsitellyt vernakulaariin kirjallisuuteen pohjautunut esitys. Warton ja hänen lähipiiriinsä kuuluneet tutkijat tarjoavat erityisen mahdollisuuden tarkastella, miten käsitys keskiajasta omana aikakautenaanmuodostui 1700-luvun lopulla. Tutkin Wartonin ja hänen aikalaistensa toisen vuosituhannen alusta kirjoittamia arvioita Michel de Certeaun historiografisen operaation käsitteen avulla. Se koostuu kolmesta vaiheesta: Alue määrittelee sosiaaliset riippuvuussuhteet ja vaikuttimet, jotka ohjaavat tutkimusta. Käytäntö viittaa siihen, miten historioitsija valitsee materiaalinsa ja muokkaa siitä historiankirjoituksena hahmottuvan kokonaisuuden. Lopuksi kirjoitus konkreettisena ja fyysisenä ilmiönä luo illuusion lopullisuudesta ja huonosti sopivien osien yhteenkuuluvuudesta. de Certeaun teoria soveltuu paremmin vanhemman historiankirjoituksen ja oppineisuuden tarkasteluun kuin historiantutkimuksen narratiiveja analysoivat teokset, koska se kontekstualisoi laajemmin historiankirjoitukseen vaikuttavat ilmiöt. Thomas Warton ja muut 1700-luvun puolivälin oppineet määrittelivät keskiajan fiktiivisten tekstien avulla. Warton tutustui tarkasti romansseihin ja kronikoihin. Erityisen suuri merkitys keskiajan hahmottamisen kannalta oli Geoffrey Monmouthilaisen kronikalla Historia regum britanniae, joka esitteli Englannin myyttisen varhaisen historian yhdistämällä Rooman ja oman kansallisen perinteen. Geoffreyn kronikan avulla Warton huomasi keskiaikaisten tarinoiden laajan vaikutuksen; hän kirjoitti erityisesti kuningas Arthuriin liittyneiden kertomusten merkityksestä, joka jatkui aina 1500-luvulle asti. Näin Warton löysi antiikin perinteelle haastajan keskiaikaisesta kulttuurista. Wartonin tapa esitellä keskiaikaa perustui osittain valistusajan sulavasti kirjoitetuille universaalihistorioille, osittain oppineelle luettelomaiselle esitystavalle. Käytännössä Wartonin pitkät johdantotutkielmat kuitenkin johdattavat lukijaa keskeisiin teemoihin. Niitä ovat mielikuvituksen väheneminen uusimmassa kirjallisuudessa ja toisaalta hienostuneisuuden ja tiedon kasvu. Warton ei missään vaiheessa kerro, liittyvätkö nämä teemat yhteen, mutta tulkintani mukaan ne liittyivät. Warton ajatteli kirjallisuuden menettäneen olennaisen mielikuvituksen samaan aikaan, kun yhteiskunta oli kehittynyt. Tämä auttaa hahmottamaan koko kirjallisuuden historiaa: Warton etsi alkuperäistä mielikuvitusta niin antiikin Kreikasta, Orientista kuin muinaisesta Skandinaviasta. History of English Poetry ei pohtinut vain kirjallisuuden ja yhteiskunnan suhdetta, sillä Warton ajatteli voivansa tutkia keskiajan yhteiskuntaa kronikoiden ja romanssien avulla. Hänen käsityksensä feodalismista, hovien elämästä ja keskiaikaisista tavoista perustuivat niihin. Warton ei huomannut, että hänen käyttämänsä lähteet olivat tietoisia kirjallisia konstruktioita vaan hän piti niitä totuudenmukaisina kuvauksina. Toisaalta Wartonin tulkintaan heijastuivat myös 1700-luvun käsitykset yhteiskunnasta. Keskiajan lähteiden kuvaukset ja 1700-luvun ideaalit vaikuttivat lopulta siihen, millaiseksi populaari kuva keskiajasta kehittyi.

Talvivaaran Kaivososakeyhtiö Oyj:n yhteiskuntavastuuraportoinnin kehittäminen

Talvivaaran Kaivososakeyhtiö Oyj:n tavoitteena on julkaista yhtiön ensimmäinen yhteiskuntavastuuraportti vuonna 2011. Vastuuraportin tavoitteena on täyttää GRI (Global Reporting Initiative) -ohjeiston C-tason raportointivaatimukset. Diplomityö liittyy olennaisena osana Talvivaaran yhteiskuntavastuuraportoinnin kehittämiseen. Diplomityön tavoitteena oli määrittää Talvivaaran ensimmäiseen raporttiin soveltuvat GRI-ohjeiston mukaiset mittarit. Työssä tarkastellaan Talvivaaran vuosikertomusta 2009. Työssä selvitettiin kuinka raporttia tulisi täydentää, jotta se täyttäisi GRI:n perussisällön C-tason vaatimukset. Näiden lisäksi työssä tehtiin sidosryhmäkartoitus, jossa selvitettiin yhtiön näkemys sidosryhmien odotuksista. Tulevaan vastuuraporttiin suunniteltujen mittareiden valintaan vaikutti sidosryhmien kiinnostuksen lisäksi se, kuinka olennaisia mittarit ovat Talvivaaran toiminnan kannalta. Valittujen mittareiden osalta yhtiön tuleva vastuuraportti täyttää selvästi C-tason raportointivaatimukset. Työssä annetaan ehdotus jatkotoimenpiteistä, joilla viestintää voidaan edelleen kehittää.

Spare part business analysis and development

The purpose of this Thesis was to comprehensively analyze and develop the spare part business in Company Oy’s five biggest product groups by searching development issues related to single spare parts’ supply chains as well as the spare part business process, make implementation plans for them and implement the plans when possible. The items were classified based on special characteristics of spare parts and on their actual sales volumes. The created item classes were examined for finding improvement possibilities. Management strategies for classified items were suggested. Vendors and customers were analyzed for supporting the comprehensive supply network development work. The effectiveness of the current spare part business process was analyzed in co-operation with the spare part teams in three business unit locations. Several items were taken away from inventories as uselessly stocked items. Price list related to core items with one of the main product group’s core item manufacturer was suggested to be expanded in Town A. Refinement equipment seal item supply chain management was seen important to develop in Town B. A new internal business process model was created for minimizing and enhancing the internal business between Company’s business units. SAP inventory reports and several other features were suggested to be changed or developed. Also the SAP data material management was seen very important to be developed continuously. Many other development issues related to spare parts’ supply chains and the work done in the business process were found. The need for investigating the development possibilities deeper became very clear during the project.

Applications of graph transformation in tools for domain-specific modeling languages

The use of domain-specific languages (DSLs) has been proposed as an approach to cost-e ectively develop families of software systems in a restricted application domain. Domain-specific languages in combination with the accumulated knowledge and experience of previous implementations, can in turn be used to generate new applications with unique sets of requirements. For this reason, DSLs are considered to be an important approach for software reuse. However, the toolset supporting a particular domain-specific language is also domain-specific and is per definition not reusable. Therefore, creating and maintaining a DSL requires additional resources that could be even larger than the savings associated with using them. As a solution, di erent tool frameworks have been proposed to simplify and reduce the cost of developments of DSLs. Developers of tool support for DSLs need to instantiate, customize or configure the framework for a particular DSL. There are di erent approaches for this. An approach is to use an application programming interface (API) and to extend the basic framework using an imperative programming language. An example of a tools which is based on this approach is Eclipse GEF. Another approach is to configure the framework using declarative languages that are independent of the underlying framework implementation. We believe this second approach can bring important benefits as this brings focus to specifying what should the tool be like instead of writing a program specifying how the tool achieves this functionality. In this thesis we explore this second approach. We use graph transformation as the basic approach to customize a domain-specific modeling (DSM) tool framework. The contributions of this thesis includes a comparison of di erent approaches for defining, representing and interchanging software modeling languages and models and a tool architecture for an open domain-specific modeling framework that e ciently integrates several model transformation components and visual editors. We also present several specific algorithms and tool components for DSM framework. These include an approach for graph query based on region operators and the star operator and an approach for reconciling models and diagrams after executing model transformation programs. We exemplify our approach with two case studies MICAS and EFCO. In these studies we show how our experimental modeling tool framework has been used to define tool environments for domain-specific languages.

Methods for construction and analysis of computational models in systems biology : applications to the modelling of the heat shock response and the self-assembly of intermediate filaments

Systems biology is a new, emerging and rapidly developing, multidisciplinary research field that aims to study biochemical and biological systems from a holistic perspective, with the goal of providing a comprehensive, system- level understanding of cellular behaviour. In this way, it addresses one of the greatest challenges faced by contemporary biology, which is to compre- hend the function of complex biological systems. Systems biology combines various methods that originate from scientific disciplines such as molecu- lar biology, chemistry, engineering sciences, mathematics, computer science and systems theory. Systems biology, unlike “traditional” biology, focuses on high-level concepts such as: network, component, robustness, efficiency, control, regulation, hierarchical design, synchronization, concurrency, and many others. The very terminology of systems biology is “foreign” to “tra- ditional” biology, marks its drastic shift in the research paradigm and it indicates close linkage of systems biology to computer science. One of the basic tools utilized in systems biology is the mathematical modelling of life processes tightly linked to experimental practice. The stud- ies contained in this thesis revolve around a number of challenges commonly encountered in the computational modelling in systems biology. The re- search comprises of the development and application of a broad range of methods originating in the fields of computer science and mathematics for construction and analysis of computational models in systems biology. In particular, the performed research is setup in the context of two biolog- ical phenomena chosen as modelling case studies: 1) the eukaryotic heat shock response and 2) the in vitro self-assembly of intermediate filaments, one of the main constituents of the cytoskeleton. The range of presented approaches spans from heuristic, through numerical and statistical to ana- lytical methods applied in the effort to formally describe and analyse the two biological processes. We notice however, that although applied to cer- tain case studies, the presented methods are not limited to them and can be utilized in the analysis of other biological mechanisms as well as com- plex systems in general. The full range of developed and applied modelling techniques as well as model analysis methodologies constitutes a rich mod- elling framework. Moreover, the presentation of the developed methods, their application to the two case studies and the discussions concerning their potentials and limitations point to the difficulties and challenges one encounters in computational modelling of biological systems. The problems of model identifiability, model comparison, model refinement, model inte- gration and extension, choice of the proper modelling framework and level of abstraction, or the choice of the proper scope of the model run through this thesis.