Líquido iônico [bmim.PF6] como solvente: um meio conveniente para estudos por fotólise por pulso de laser

The spectroscopic behavior of thioxanthone and benzil (diphenylethanedione or dibenzoyl) in the ionic liquid [bmim.PF6] has been investigated employing the laser flash photolysis technique. Triplet-triplet absorption spectra for these carbonyl compounds in [bmim.PF6] are similar to those observed in organic solvents. The triplet lifetime for thioxanthone in desogygenated samples is very long (71 μs), whereas in oxygen-saturated solution is 500 ns, which indicates the low oxygen solubility in this solvent. For benzil, lifetimes of 10 μs in [bmim.PF6] and 3.8 μs in acetonitrile were obtained. The decay for triplet thioxanthone and benzil follows a clear first order kinetics in [bmim.PF6], from which one can conclude that triplet-triplet annihilation is not an important decay process in this solvent.

Simulação Monte Carlo no ensino de luminescência e cinética de decaimento de estados excitados

A software based in the Monte Carlo method have been developed aiming the teaching of important cases of mechanisms found in luminescence and in excited states decay kinetics, including: multiple decays, consecutive decays and coupled systems decays. The Monte Carlo Method allows the student to easily simulate and visualize the luminescence mechanisms, focusing on the probabilities of the related steps. The software CINESTEX was written for FreeBASIC compiler; it assumes first-order kinetics and any number of excited states, where the pathways are allowed with probabilities assigned by the user.

Foam-forming properties of Ilex paraguariensis (mate) saponin: foamability and foam lifetime analysis by Weibull equation

Saponins are natural soaplike foam-forming compounds widely used in foods, cosmetic and pharmaceutical preparations. In this work foamability and foam lifetime of foams obtained from Ilex paraguariensis unripe fruits were analyzed. Polysorbate 80 and sodium dodecyl sulfate were used as reference surfactants. Aiming a better data understanding a linearized 4-parameters Weibull function was proposed. The mate hydroethanolic extract (ME) and a mate saponin enriched fraction (MSF) afforded foamability and foam lifetime comparable to the synthetic surfactants. The linearization of the Weibull equation allowed the statistical comparison of foam decay curves, improving former mathematical approaches.

Electrochemical study, on mercury, of a Meta-nitroarylamine derivative of nor-β-lapachone, an antitumor and trypanocidal compound

The electrochemistry of 2,2-dimethyl-(3H)-3-(N-3'-nitrophenylamino)naphtho[1,2- b]furan-4,5-dione ([Q]-PhNO2), on mercury was investigated. The first peak is consistent with a quasi-reversible one-electron reduction of the ortho-quinone, forming [Q•-]-PhNO2, while the second one, bielectronic, corresponds to the simultaneous reduction of the latter radical to a dianion and the nitro group to a nitro radical anion. The second order rate constant, k disp, for the decay of [Q•-]-PhNO2 is 15.188 x 10³ ± 827 mol"1 L s"1 and the t1/2 equals 0.06 s. E¹7Ic values for [Q]-PhNO2 and its precursor, nor-β-lapachone, are similar. The ease of semiquinone generation and its stability are parameters statistically relevant in the correlation biochemical/theoretical aspects.

Simulação Monte Carlo de mecanismo de transferência de energia de excitação eletrônica: modelo de Perrin para a supressão estática da luminescência

A software based in the Monte Carlo method has been developed aiming the teaching of the Perrin´s model for static luminescence quenching. This software allows the student to easily simulate the luminescence decays of emissive molecules in the presence of quenching ones. The software named PERRIN was written for FreeBASIC compiler and it can be applied for systems where the molecules remain static during its excited state lifetime. The good agreement found between the simulations and the expected theoretical results shows that it can be used for the luminescence and excited states decay kinetic teaching.

Degradação fotoeletroquímica do herbicida bentazona sobre eletrodos de carbono modificados por TiO2

This work involved the study of degradation of the herbicide bentazone in aqueous solution by different routes, in order to search a method that generates safe products to the environment. It was tested electrochemical polarization methods involving positive and negative potential, irradiation with UV light and deposition of TiO2 on the electrode surface, seeking a catalytic effect. After different times of degradation, aliquots were removed and the scan of molecular absorption spectrum of UV-Vis was performed. From the spectra decay of bentazone, the kinetics of different processes was accompanied and the rate constants were determined.

Ligniinin määrän ja ligniinin modifioinnin vaikutus kuusen puuaineen ominaisuuksiin ja lahonkestoon

Seloste väitöskirjasta: The effect of lignin content and lignin modification on Norway spruce wood properties and decay resistance. Dissertationes Forestales 68.

Decaimento de íons cianato e a formação de carbamato de etila

Cyanate ion stability was studied in aqueous/ethanolic solutions, pH = 4.5 (CH3COOH/NaCH3COO), at different temperatures. Following the decay [(OCN)-] versus time, in the presence of excess C2H5OH, the rate constant for this reaction (k1) was calculated as (2.5 ± 0.3) x 10-4 s-1 at 25 ºC, for 0 < [C2H5OH] < 13.7 x 10-1 mol L-1. For [C2H5OH] > 2.0 mol L-1 a decrease in the numerical value of k1 was observed, reaching 5.2 x 10-5 s-1 when [CH3CH2OH] = 13.7 mol L-1. Variations in the kinetic parameter values ΔH1‡, ΔS1‡ and ΔG1‡ for the cyanate ion decay reaction were observed for solutions at different ethanol concentrations.

Software para simulação de mecanismo de supressão da luminescência: modelo cinético de Stern-Volmer

A software that includes both Stochastic and Molecular Dynamics procedures has been developed with the aim of visualizing the Stern-Volmer kinetic mechanism of dynamic luminescence quenching. The software allows the student to easily simulate and graphically visualize the molecular collisions, the molecular speed distributions, the luminescence decay curves, and the Stern-Volmer graphs. The software named "SternVolmer" is written for the FreeBASIC compiler and can be applied to dynamic systems where luminescent molecules, during their excited state lifetimes, are able to collide with quenching molecules (collisional quenching). The good agreement found between the simulations and the expected results shows that this software can be used as an effective teaching aid for the study of luminescence and kinetic decay of excited states.

Time-Resolved Photoluminescence in Antimonide and Dilute Nitride Quantum Well Structures

This Master's thesis is devoted to semiconductor samples study using time-resolved photoluminescence. This method allows investigating recombination in semiconductor samples in order to develop quality of optoelectronic device. An additional goal was the method accommodation for low-energy-gap materials. The first chapter gives a brief intercourse into the basis of semiconductor physics. The key features of the investigated structures are noted. The usage area of the results covers saturable semiconductor absorber mirrors, disk lasers and vertical-external-cavity surface-emittinglasers. The experiment set-up is described in the second chapter. It is based on up-conversion procedure using a nonlinear crystal and involving the photoluminescent emission and the gate pulses. The limitation of the method was estimated. The first series of studied samples were grown at various temperatures and they suffered rapid thermal annealing. Further, a latticematched and metamorphically grown samples were compared. Time-resolved photoluminescence method was adapted for wavelengths up to 1.5 µm. The results allowed to specify the optimal substrate temperature for MBE process. It was found that the lattice-matched sample and the metamorphically grown sample had similar characteristics.

Dental Health in Primary Teeth after Prevention of Mother-Child Transmission of Mutans Streptococci. A Historical Cohort Study on Restorative Visits and Maternal Prevention Costs

Mutansstreptokokkitartunnan ehkäisemisen pitkäaikaisvaikutukset maitohampaiden terveyteen. Kohorttitutkimus korjaavan hoidon määrästä ja kariesehkäisyn kustannuksista. Tutkimuksen tarkoituksena oli selvittää varhaisen mutansstreptokokki (MS)-kolonisaation ehkäisyn pitkäaikaisvaikutuksia korkean kariesriskin omaavien lasten maitohampaistossa sekä tarkastella MS-tartunnan estämisen kustannuksia. Tiedot lasten hampaiden terveydestä ja hammashoitotoimenpiteistä syntymästä 10-vuotiaaksi sekä äiteihin kohdistuneen kariesehkäisyn kustannuksista kerättiin Ylivieskan terveyskeskuksen asiakirjoista. Tutkimuksessa oli mukana yhteensä 507 lasta, heistä 148 oli osallistunut aikaisempaan Ylivieskan äiti-lapsitutkimukseen, jossa verrattiin äitien käyttämän ksylitolipurukumin ja äidille tehtyjen fluori- tai klooriheksidiinilakkausten vaikutusta pikkulasten hampaiden terveyteen. Maitohammaskariesta esiintyi 10-vuotiaaksi asti merkitsevästi vähemmän lapsilla, jotka eivät olleet saaneet MS-tartuntaa alle 2-vuotiaana, heidän maitohampaansa säilyivät 3,4 vuotta kauemmin täysin ehjinä (p<0.001) ja he tarvitsivat vähemmän maitohampaiden korjaavaa hoitoa (p=0.005) kuin lapset, joiden hampaisto oli kolonisoitunut MS-bakteerilla jo 2-vuotiaana. Koska ksylitoliryhmän lasten MS-kolonisaatio oli vähäisintä, heidän maitohampaissaan oli vähemmän kariesta ja korjaavan hoidon tarvetta kuin kahden muun korkeariskisen ryhmän lapsilla. Äitien käyttämän ksylitolipurukumin kustannukset olivat yhteensä 116 euroa ja lapsen maitohampaiden säilyminen täysin ehjinä vuoden pidempään maksoi 37 euroa. Kun MS-tartunta oli saatu estettyä, korkean kariesriskin omaavien lasten hampaiden terveys oli samalla tasolla kuin keskimäärin koko ikäkohortilla. Lapsen maitohampaat säilyvät terveinä pidempään ja korjaavan hoidon tarve vähenee, kun MS-kolonisaatio alle 2-vuotiaana saadaan estettyä. Lapsen MS-kolonisaatio vähenee merkitsevästi, kun äiti käyttää ksylitolipurukumia lapsen ollessa 0-2 vuoden ikäinen, siten pikkulapsen äidin säännöllinen ksylitolipurukumin käyttö saattaa olla julkisen tereydenhuollon kannalta tarkoituksenmukainenterveyttä edistävä menetelmä.

Metaanin muodostumisen mallintaminen kaatopaikalla

Methane-rich landfill gas is generated when biodegradable organic wastes disposed of in landfills decompose under anaerobic conditions. Methane is a significant greenhouse gas, and landfills are its major source in Finland. Methane production in landfill depends on many factors such as the composition of waste and landfill conditions, and it can vary a lot temporally and spatially. Methane generation from waste can be estimated with various models. In this thesis three spreadsheet applications, a reaction equation and a triangular model for estimating the gas generation were introduced. The spreadsheet models introduced are IPCC Waste Model (2006), Metaanilaskentamalli by Jouko Petäjä of Finnish Environment Institute and LandGEM (3.02) of U.S. Environmental Protection Agency. All these are based on the first order decay (FOD) method. Gas recovery methods and gas emission measurements were also examined. Vertical wells and horizontal trenches are the most commonly used gas collection systems. Emission measurements chamber method, tracer method, soil core and isotope measurements, micrometeorological mass-balance and eddy covariance methods and gas measuring FID-technology were discussed. Methane production at Ämmässuo landfill of HSY Helsinki Region Environmental Services Authority was estimated with methane generation models and the results were compared with the volumes of collected gas. All spreadsheet models underestimated the methane generation at some point. LandGEM with default parameters and Metaanilaskentamalli with modified parameters corresponded best with the gas recovery numbers. Reason for the differences between evaluated and collected volumes could be e.g. that the parameter values of the degradable organic carbon (DOC) and the fraction of decomposable degradable organic carbon (DOCf) do not represent the real values well enough. Notable uncertainty is associated with the modelling results and model parameters. However, no simple explanation for the discovered differences can be given within this thesis.

Studies on the Multifaceted Interaction of Atoms and an Electromagnetic Field

In this Thesis the interaction of an electromagnetic field and matter is studied from various aspects in the general framework of cold atoms. Our subjects cover a wide spectrum of phenomena ranging from semiclassical few-level models to fully quantum mechanical interaction with structured reservoirs leading to non-Markovian open quantum system dynamics. Within closed quantum systems, we propose a selective method to manipulate the motional state of atoms in a time-dependent double-well potential and interpret the method in terms of adiabatic processes. Also, we derive a simple wave-packet model, based on distributions of generalized eigenstates, explaining the finite visibility of interference in overlapping continuous-wave atom lasers. In the context of open quantum systems, we develop an unraveling of non-Markovian dynamics in terms of piecewise deterministic quantum jump processes confined in the Hilbert space of the reduced system - the non-Markovian quantum jump method. As examples, we apply it for simple 2- and 3-level systems interacting with a structured reservoir. Also, in the context of ion-cavity QED we study the entanglement generation based on collective Dicke modes in experimentally realistic conditions including photonic losses and an atomic spontaneous decay.

On convergence of transforms based on parabolic scaling

This thesis studies properties of transforms based on parabolic scaling, like Curvelet-, Contourlet-, Shearlet- and Hart-Smith-transform. Essentially, two di erent questions are considered: How these transforms can characterize H older regularity and how non-linear approximation of a piecewise smooth function converges. In study of Hölder regularities, several theorems that relate regularity of a function f : R2 → R to decay properties of its transform are presented. Of particular interest is the case where a function has lower regularity along some line segment than elsewhere. Theorems that give estimates for direction and location of this line, and regularity of the function are presented. Numerical demonstrations suggest also that similar theorems would hold for more general shape of segment of low regularity. Theorems related to uniform and pointwise Hölder regularity are presented as well. Although none of the theorems presented give full characterization of regularity, the su cient and necessary conditions are very similar. Another theme of the thesis is the study of convergence of non-linear M ─term approximation of functions that have discontinuous on some curves and otherwise are smooth. With particular smoothness assumptions, it is well known that squared L2 approximation error is O(M-2(logM)3) for curvelet, shearlet or contourlet bases. Here it is shown that assuming higher smoothness properties, the log-factor can be removed, even if the function still is discontinuous.