Viologeenit sensorimateriaaleissa

Pro gradu -työn taustalla oli selvittää sähkökemiallisella polymeroinnilla tuotetun viologeenikalvon anioniselektiivisyyttä. Polymerointi toteutettiin sekä staattisella kennosysteemillä että suihkuvirtauskennolla (engl. wall-jet) käyttäen 1,3,5-tris-(N-metyyli-4-syanopyridinium)-2,4,6-trimetyylitribromidi-, trans-1,2-bis-(karbamoyyli-para-metyylisyano-pyridinium)-sykloheksaanidibromidi- ja 1,3-bis-[4-(para-metyylisyanopyridinium)-fenyyli-tioureido]-ksyleenidibromidilähtöaineita. Platina- ja kultasubstraateille muodostettuja viologeenikalvoja tutkittiin voltammetrisesti (CV), kronoamperometrisesti (CA), konduktometrisesta (GA) sekä kvartsikidemikrovaakaa (QCMB) apuna käyttäen. Tulosten perusteella polymeerirakenteet omasivat anionikaviteetteja mutta affiniteetit eri anionien väillä eivät korreloineet täydellisesti sähkökemiallisessa generoinnissa käytettyjen muotti-ionien kanssa. Selektiivisyyteen todennäköisesti vaikuttivat myös liuosfaasissa olleiden ionisten molekyylien ja solvatoituneiden anionien poolisuus ja hydraattiverhon koko. Lisäksi polymeroitujen viologeenien anionivakansseista suurin osa todettiin inaktiivisiksi. Kirjallisuuskatsauksen perusteella substituoidut γ,γ’-bipyridyylit ovat materiaaleina lupaavia ja yleisen sensoriteknologian mielenkiinnon kohteena mm. aurinkokennoissa, biosensoreissa ja elektronin delokalisaatioon perustuvissa värinäytöissä (ECD). Ongelmina löydetyissä sovellutuksissa ovat olleet bipyridyylien vuotaminen liuokseen, katalyyttisesti verraten hitaat elektroninsiirtoreaktiot ja yhdisteiden myrkyllisyys. Vastaavasti etuja ovat olleet polymeerien intensiiviset värit, väriskaalan muokattavuus, sähkökemiallisesti tuotetun radikaalikationin stabiilius vesiliuoksessa, katalyyttinen aktiivisuus ja helppo synteesireitti syanopyridiinilähtöaineista.

A broadband leptonic model for gamma-ray emitting microquasars

Observational and theoretical studies point to microquasars (MQs) as possible counterparts of a significant fraction of the unidentified gamma-ray sources detected so far. At present, a proper scenario to explain the emission beyond soft X-rays from these objects is not known, nor what the precise connection is between the radio and the high-energy radiation. We develop a new model where the MQ jet is dynamically dominated by cold protons and radiatively dominated by relativistic leptons. The matter content and power of the jet are both related with the accretion process. The magnetic field is assumed to be close to equipartition, although it is attached to and dominated by the jet matter. For the relativistic particles in the jet, their maximum energy depends on both the acceleration efficiency and the energy losses. The model takes into account the interaction of the relativistic jet particles with the magnetic field and all the photon and matter fields. Such interaction produces significant amounts of radiation from radio to very high energies through synchrotron, relativistic Bremsstrahlung, and inverse Compton (IC) processes. Variability of the emission produced by changes in the accretion process (e.g. via orbital eccentricity) is also expected. The effects of the gamma-ray absorption by the external photon fields on the gamma-ray spectrum have been taken into account, revealing clear spectral features that might be observed. This model is consistent to the accretion scenario, energy conservation laws, and current observational knowledge, and can provide deeper physical information of the source when tested against multiwavelength data.

Crassostrea patagonica (d'Orbigny, 1842) shell concentrations from the late Miocene Rio Negro province, NE Patagonia, Argentina

The Río Negro Formation (late Miocene-early Pliocene) mainly consists of continental deposits, but it contains a middle member of marine origin. It represents a transgressive-regressive sequence that can be seen at several outcrops along the N Patagonian coast. The taphonomical approach to the El Espigón marine deposits permits the identification of four main layers containing different kinds of skeletal accumulation, which mainly consist of oyster shells [Crassostrea patagonica (D'Orbigny, 1842)]. These concentrations display three different morphologies (pouches, pavements and bouquets) with a different taphonomic signature. These deposits were formed in shallow marine environments influenced by wave activity that produced valve concentrations of different entities. They contain several shell beds that represent event, composite, hiatal to lag skeletal concentrations. Traces of bioturbation in the sediment (Thalassinoides, Teichichnus) and bioerosion on the shells (Entobia, Gastrochaeonolites, Caulostrepsis), and encrusters (cirripeds, bryozoans), are also abundant in the outcrop and consititue common components of these Miocene materials. Layers 1 and 2 of the sequence were deposited in shoreface/foreshore environments at the beginning of a highstand systems tract, while layers 3 and 4 were deposited at the end, or at the beginning of a forced regression, in foreshore environments. A final erosional episode cut the top of the layer 4, which truncated the abundant bioturbaation developed there.

The age of the"Grande Coupure" mammal turnover: New constraints from the Eocene Oligocene record of the Eastern Ebro Basin (NE Spain.)

The Grande Coupure represents a major terrestrial faunal turnover recorded in Eurasia associated with the overall climate shift at the Eocene-Oligocene transition. During this event, a large number of European Eocene endemic mammals became extinct and new Asian immigrants appeared. The absolute age of the Grande Coupure, however, has remained controversial for decades. The Late Eocene-Oligocene continental record of the Eastern Ebro Basin (NE Spain) constitutes a unique opportunity to build a robust magnetostratigraphy- based chronostratigraphy which can contribute with independent age constraints for this important turnover. This study presents new magnetostratigraphic data of a 495-m-thick section (Moià-Santpedor) that ranges from 36.1 Ma to 33.3 Ma. The integration of the new results with previous litho- bio- and magnetostratigraphic records of the Ebro Basin yields accurate ages for the immediately pre- and post-Grand Coupure mammal fossil assemblages found in the study area, bracketing the Grande Coupure to an age embracing the Eocene-Oligocene transition, with a maximum allowable lag of 0.5 Myr with respect to this boundary. The shift to drier conditions that accompanied the global cooling at the Eocene-Oligocene transition probably determined the sedimentary trends in the Eastern Ebro Basin. The occurrence and expansion of an amalgamated-channel sandstone unit is interpreted as the forced response of the fluvial fan system to the transient retraction of the central-basin lake systems. The new results from the Ebro Basin allow us to revisit correlations for the controversial Eocene-Oligocene record of the Hampshire Basin (Isle of Wight, UK), and their implications for the calibration of the Mammal Palaeogene reference levels MP18 to MP21.

Non-thermal emission from microquasar/ISM interaction

Context. The interaction of microquasar jets with their environment can produce non-thermal radiation as in the case of extragalactic outflows impacting on their surroundings. Significant observational evidence of jet/medium interaction in galactic microquasars has been collected in the past few years, although little theoretical work has been done regarding the resulting non-thermal emission. Aims. In this work, we investigate the non-thermal emission produced in the interaction between microquasar jets and their environment, and the physical conditions for its production. Methods. We developed an analytical model based on those successfully applied to extragalactic sources. The jet is taken to be a supersonic and mildly relativistic hydrodynamical outflow. We focus on the jet/shocked medium structure in its adiabatic phase, and assume that it grows in a self-similar way. We calculate the fluxes and spectra of the radiation produced via synchrotron, inverse Compton, and relativistic bremsstrahlung processes by electrons accelerated in strong shocks. A hydrodynamical simulation is also performed to investigate further the jet interaction with the environment and check the physical parameters used in the analytical model. Results. For reasonable values of the magnetic field, and using typical values of the external matter density, the non-thermal particles could produce significant amounts of radiation at different wavelengths, although they do not cool primarily radiatively, but by adiabatic losses. The physical conditions of the analytical jet/medium interaction model are consistent with those found in the hydrodynamical simulation. Conclusions. Microquasar jet termination regions could be detectable at radio wavelengths for current instruments sensitive to ~arcminute scales. At X-ray energies, the expected luminosities are moderate, although the emitter is more compact than the radio one. The source may be detectable by XMM-Newton or Chandra, with 1-10 arcsec of angular resolution. The radiation at gamma-ray energies may be within the detection limits of the next generation of satellite and ground-based instruments.

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

Uso da pressão gerada por uma coluna de água para controle da vazão em sistemas de análises em fluxo

This work presents a new approach to control the flow rate in hydrodynamic flow experiments. The combination of air pressure generated by an aquarium air pump and the pressure generated by a water column were used for this purpose. This device supports a stable flow rate without pulsation for a long period of time. Furthermore, the flow rate can be easily controlled at various values in one or more streams. The performance of this approach was investigated using Fe(CN)6(4-) solutions in flowing systems using amperometric and voltammetric detection in wall-jet configuration. The results showed that the performance of the proposed device was better than a commercial peristaltic pump. It suggests that this approach can be used successfully in flow analysis systems.

Kehittyneiden hitsausprosessien soveltuvuus alumiinin ja hiiliterästen hitsaukseen

Diplomityössä tutkitaan hitsausprosessien kehitystä. Työn kirjallisen osan alku kuvaa hitsauksen nykypäivää ja tulevaisuutta sekä millainen on hitsaava Suomi. Kehittyneiden hitsausprosessien tarkastelu on jaettu hiiliterästen ja alumiinien hitsausprosesseihin. Hiiliteräksien hitsauksen osalta työssä esitellään kitkahitsaus pyörivällä työkalulla, muunnettu lyhytkaarihitsaus, laserhitsaus, laser-hybridihitsaus ja kapearailohitsaus. Alumiinien hitsauksen osalta työssä esitellään laserhitsaus, muunnettu lyhytkaarihitsaus, kitkahitsaus pyörivällä työkalulla ja vaihtovirta MIG hitsaus. Diplomityön käytännönosuudessa todennettiin hitsausprosessien kehitys. Ensimmäisissä hitsauskokeissa hitsattiin merialumiinia eri kaarityypeillä. Vertailua tehdään pulssihitsauksen, lankapulssihitsauksen sekä CMT-kaarihitsauksen välillä. Koehitsaukset osoittavat CMT-hitsauksen tuottavan MIG-pulssihitsausta pienemmät hitsausmuodonmuutokset. CMT-hitsauksessa alumiinin oksidikerros aiheuttaa MIGpulssihitsausta vähemmän ongelmia, sillä kaari syttyy varmemmin suurillakin hitsausnopeuksilla, eikä hitsiin synny huokosia. Hitsausnopeudella 40 cm/min lankapulssihitsauksella ja MIG-pulssihitsauksella päittäisliitoksena hitsattujen vesileikattujen alumiinikappaleiden hitseihin ei syntynyt huokosia. Kokeen perusteella voidaan todeta, ettei oksidikerroksella ollut vaikutusta hitsin onnistumiseen. Hitsauskokeiden toinen osio tutkii hiilimangaaniteräksisen T-palkin kuitulaserhitsausta. Viiden kilowatin laserteholla hitsattiin onnistuneesti viisi metriä pitkiä T-palkkeja hitsausnopeudella 2 m/min. Takymetrimittauksella ja Tritop 3D-koordinaattimittauksella todennettiin laserhitsatun T-palkin hitsausmuodonmuutosten olevan huomattavasti Twin-jauhekaarihitsauksella hitsattua T-palkkia pienemmät.

Construção de um sistema simples e compacto de recirculação d'água sob pressão para trompa d'água

Vacuum pumps are very useful in physical, chemical and biological experiments. In this communication it is described the design of a compact and low cost water recirculating system employing a water-jet aspirator pump as the vacuum source. The system requires only a water pump, water-jet aspirator pump, commercial PVC water tubes and a drain connection.

Construção e caracterização de um detector eletroquímico para análises em fluxo

The present work describes a low-cost electrochemical "wall-jet" detector for flow analysis. The electrolytic solution enters into the cell through a tube of stainless steel (200 to 300 µm i.d), reaching to the center of the working electrode perpendicularly and then being mixed to the remaining solution in the cell, which flows under atmospheric pressure into a waste reservoir. The proposed electrochemical detector can be used with any type of working electrode, from commercial to home-made, such as glassy carbon and metallic electrodes (modified or unmodified), which enlarge the applications of the electrochemical detector.

Processamento de cartuchos de impressoras de jato de tinta: um exemplo de gestão de produto pós-consumo

This work presents a route for processing spent ink-jet cartridges in an experimental course. The disassembly of the cartridges requires several steps and the recognition of their different components is essential to define the best final destination (recycling, co-processing). The plastic strips were chemically processed so as to recover gold and copper. The students recognized the difficulty of processing multicomponent wastes and the importance of the chemical work under the best safety conditions; they also experienced many laboratory techniques and recognized the value of the selective collection and the reverse logistics to reach a viable commercial scale recycling.

Química e sustentabilidade: novas fronteiras em biocombustíveis

This contribution discusses the state of the art and the challenges in producing biofuels, as well as the need to develop chemical conversion processes of CO2 in Brazil. Biofuels are sustainable alternatives to fossil fuels for providing energy, whilst minimizing the effects of CO2 emissions into the atmosphere. Ethanol from fermentation of simple sugars and biodiesel produced from oils and fats are the first-generation of biofuels available in the country. However, they are preferentially produced from edible feedstocks (sugar cane and vegetable oils), which limits the expansion of national production. In addition, environmental issues, as well as political and societal pressures, have promoted the development of 2nd and 3rd generation biofuels. These biofuels are based on lignocellulosic biomass from agricultural waste and wood processing, and on algae, respectively. Cellulosic ethanol, from fermentation of cellulose-derived sugars, and hydrocarbons in the range of liquid fuels (gasoline, jet, and diesel fuels) produced through thermochemical conversion processes are considered biofuels of the new generation. Nevertheless, the available 2nd and 3rd generation biofuels, and those under development, have to be subsidized for inclusion in the consumer market. Therefore, one of the greatest challenges in the biofuels area is their competitive large-scale production in relation to fossil fuels. Owing to this, fossil fuels, based on petroleum, coal and natural gas, will be around for many years to come. Thus, it is necessary to utilize the inevitable CO2 released by the combustion processes in a rational and economical way. Chemical transformation processes of CO2 into methanol, hydrocarbons and organic carbonates are attractive and relatively easy to implement in the short-to-medium terms. However, the low reactivity of CO2 and the thermodynamic limitations in terms of conversion and yield of products remain challenges to be overcome in the development of sustainable CO2 conversion processes.

Koneinvestoinnin suunnittelu valmistavaan teollisuuteen

Tämän diplomityön tavoitteena oli tutustua ohutlevyjen nykyaikaisiin koneellisiin leikkausmenetelmiin ja tutkia niiden soveltuvuutta yrityksen tarpeisiin. Kohdeyrityksessä investoinnin tarve jakautui tuottavuusinvestoinnin, korvausinvestoinnin ja strategisen investoinnin kesken. Tavoitteena oli luoda investointipolku, jonka avulla poissuljettiin menetelmät, jotka eivät soveltuneet yrityksen tuotantoon. Työn kirjallisuusosuudessa tarkastellaan teoriatietoja, jotka liittyvät yleisesti nykyaikaisiin ohutlevyjen leikkausmenetelmiin sekä investointiprojektin suunnitteluun ja toteutuksen teoriaan. Lisäksi käsitellään investointeihin liittyviä kannattavuus- ja kustannuslaskennan perusperiaatteita. Työn empiirisessä osassa selvitettiin yrityksen ohutlevyosien valmistuksen periaatteita nykytila-analyysin avulla. Tämän perusteella määritettiin nykyaikaisista markkinoilla olevista menetelmistä yritykselle soveltuvin. Tutkimuksen perusteella laserleikkaus oli menetelmistä soveltuvin. Perusinvestoinniltaan laser oli vaihtoehtoisista menetelmistä kallein, mutta se soveltui käytettävyyden, tehokkuuden, joustavuuden ja muiden ominaisuuksiensa perusteella parhaiten tuotannon tarpeisiin. Työn merkittävimmät tulokset osoittivat, että investoinnin kannattavuus riippui koneelle saatavasta käyttösuhteesta. Uusien koneiden tehokkuus lyhentäisi tuotannon läpimenoaikoja, mutta ilman riittävää kapasiteetin käyttöastetta kappaleiden omakustannusarvo nousisi. Lopputulokset ja suositukset on esitetty työn lopussa.

Determinação amperométrica de iodeto em soluções expectorantes orais com análise por injeção em fluxo usando a reação iodeto/nitrito

Neste trabalho foi desenvolvido um sistema de injeção em fluxo visando à determinação amperométrica de íons iodeto em soluções expectorantes. O método é baseado na reação do iodeto com íons nitrito em meio ácido. O iodo formado é monitorado por amperometria no potencial de +200 mV vs. Ag/AgCl (3 mol L-1), usando um eletrodo de trabalho de disco de platina (RDE) com raio = 0,75 mm adaptado a uma célula eletroquímica "wall-jet". O sistema em fluxo foi usado com o carregador impulsionado pela pressão gravitacional dos reagentes (carregador: solução 2 x 10-4 mol L-1 em NaNO2 e 0,2 mol L-1 em H2SO4), na vazão de 4 mL min-1. O método é rápido (acima de 100 injeções h-1) e preciso (RSD = 1,9%; n=10 e C I 8 x 10-6 mol L-1), apresentando um limite de detecção de 20 ng I- ou 8 x 10-7 mol L-1 (3SD). A validação do método proposto foi realizada seguindo as normas USP, ou seja, titulação potenciométrica com AgNO3 0,100 mol L-1 e os resultados obtidos mostraramse concordantes com os valores de referência do fabricante.

Russian Venture Capital Markets

Tämän työn tarkoituksena on arvioida riskipääomasijoittamisen kehitystä ja kasvua Venäjällä, sekä antaa kuva siihen vaikuttavista tekijöistä. Se myös arvioi Venäjän valtion toimintaa niin säätelijänä, kuin myös itsenäisenä sijoittajana. Saavutetut tulokset perustuvat haastatteluihin ja olemassa olevien tilastojen analysointiin. Vuoden 1998 rupla kriisin jälkeen riskipääomasijoittaminen lähti kasvuun joka on jatkunut tasaisella rauhallisella tahdilla. Alueellisista riskipääomarahastoista on siirrytty myös yksityisrahoitteisiin ja yksityishallinnoituihin rahastoihin omine kohde aloineen ja portfolioineen. Silti markkinat ovat säilyneet kyllästymättöminä. Kuluttajavetoiset toimialat ovat keränneet eniten investointeja talouden ja ostovoiman kasvusta johtuen. Alueellisesti Moskova erottuu sijoituskohteena, muiden suurempien kasvukeskusten seuratessa perässä. Venäjällä on vielä paljon heikkouksia jotka vaikuttavat sen houkuttelevuuteen sijoittajan näkökulmasta. Heikot instituutiot ja lainsäädäntö yhdistettynä riskipääomasijoittamisen luonteeseen tekevät Venäjästä arvaamattoman markkina-alueen. Se kuitenkin tarjoaa menestyville sijoittajille korkeat tuotot. Nähtäväksi jää kuinka valtion toiminta vaikuttaa markkinoiden kehitykseen lyhyellä ja pitkällä tähtäimellä, ja kuinka se onnistuu kehittämään Venäjän yleistä kilpailukykyä globaaleilla markkinoilla.