Termocromismo em soluções de alcóxidos de Vanádio(IV): uma abordagem pela modelagem molecular

The thermochromic behavior exhibited by vanadium(IV) alkoxides, [V2(μ-OPr i)2(OPr i) 6] and [V2(μ-ONep)2(ONep)6 ], OPr i = isopropoxide and ONep = neopentoxide, was studied by molecular modeling using DFT, TDDFT and INDO/S methods. The vibrational and electronic spectra calculated for [V2(μ-OPr i)2(OPr i) 6] were very similar to the experimental data registered for crystalline samples of the complex and for its solutions at low temperature (< 210 K), while spectra recorded at high temperature (> 315 K) were compatible with those calculated for the monomeric form, [V(OPr i)4]. These results consistently point to a monomer/dimer equilibrium as an explanation for the solution thermochromism of {V(OPr i)4}n. In spite of the structural similarity between [V2(μ-ONep)2(ONep)6 ] and [V2(μ-OPr i)2(OPr i) 6] in the solid state, the thermochromic behavior of the former could not be explained by the same model, and the possibility of tetranuclear aggregation at low temperatures was also investigated.

Química e filosofia: rumo a uma frutífera colaboração

This review seeks to present a brief history of the philosophy of chemistry and the major issues discussed in the framework of this emerging discipline of philosophy of science, such as the question of physicalist reductionism and physical and chemical causality. In this vein, it also addresses the current debate over relevant issues of chemical world such as atomic orbitals, molecular structure, chemical bonding, models and explanations, as well as the foundations of the periodic table. Finally, the importance of the link between the philosophy of chemistry and chemistry education is analyzed, especially in relation to teacher training.

A NOVEL POLYACRYLAMIDE-BASED HYDROGEL CROSSLINKED WITH CELLULOSE ACETATE AND PREPARED BY PRECIPITATION POLYMERIZATION

The synthesis of polyacrylamide-cellulose acetate hydrogels by precipitation polymerization in acetone solution is reported herein. These hydrogels exhibit smaller swelling ratios and larger compression moduli than homo polyacrylamide hydrogels. For cellulose acetate concentrations above 20 wt.%, hydrogels with N,N'-methylenebisacrylamide as a crosslinker exhibit swelling ratios and compression moduli similar to those of the hydrogels without the crosslinker. A possible explanation for this behavior is that cellulose acetate crosslinks polyacrylamide via free-radical reaction. The hydrogels obtained without the N,N'-methylenebisacrylamide crosslinker exhibit compression moduli up to 1.7 MPa, making them suitable for tissue engineering applications such as cartilage replacement.

CONHECIMENTO PEDAGÓGICO E CONHECIMENTO QUÍMICO NA FORMAÇÃO DE PROFESSORES: A CONSTRUÇÃO DA IDENTIDADE DOCENTE

This paper presents results of a content analysis of the formative professional profile of undergraduates within the context of Brazil's expansion of its federal education system and implementing of teacher training policies. The analysis focuses on the conceptions of undergraduates regarding elements of their initial training and professional perspectives, as recorded in narratives, interviews, and questionnaires. Based on the relationships identified between the recorded content and the Educational Course Project, we identified three categories of analysis that point to tensions generated during the professional development of chemistry teachers: 1) The relationship between pedagogical knowledge and chemical knowledge; 2) the conceptual aspects of science education, as represented by the different ways that students understand the "ionization process"; and 3) teaching identity, including the elements indicative of the identity construction of future teachers. The results indicate that the educational and professional profile of undergraduates is marked by a particular tension between chemical content knowledge and pedagogical content, as well as a lack of objectivity and focus on the course's original intent. This situation has produced a multifaceted training context in which there is confusion regarding aspects relating to the licensing, teaching modalities, and preparation of the chemistry education professional.

Granulation tissue formation -The effect of hydroxyapatite coating of cellulose on cellular differentiation

Haavan jyväiskudoksen muodostuminen – Hydroksiapatiittipinnoi-tetun selluloosasienen vaikutus solujen erilaistumiseen paranemisprosessin aikana Etsittäessä uusia luun bioyhteensopivia täytemateriaaleja selluloosasieni päällystettiin luun koostumusta muistuttavalla runsaasti piitä sisältävällä hydroksiapatiittikerroksella. Vastoin odotuksia hydroksiapatiittipinnoitettu selluloosa ei parantanut luun kasvua, vaan päinvastoin ylläpiti tulehdusta ja sidekudossolujen hakeutumista vamma-alueelle. Ihon alle implantoituna sama sienimateriaali edisti merkittävästi haavan verekkään jyväiskudoksen kasvua. Tämän löydöksen perusteella hydroksiapatiittipinnoitetun selluloosasienen vaikutusta haavan soluihin paranemisprosessin aikana tutkittiin tarkemmin ja havaittiin, että tulehdussolujen lisäksi sieniin kertyi tavallista enemmän sekä hematopoieettisia että mesenkymaalisia kantasoluja. Hematopoieettiset kantasolut sijaitsevat luuytimessä lähellä luun sisäpintaa. Luun hydroksiapatiitista vapautuu kalsiumioneja luun jatkuvan fysiologisen uudismuodostuksen ja hajottamisen yhteydessä. Kantasolut etsiytyvät luuytimeen kalsiumia aistivien reseptorien välityksellä. Koska luun pintakerrosta muistuttavasta hydroksiapatiittipinnoitteesta vapautuu kalsiumia, tämän ajateltiin toimivan selityksenä sille, että hematopoieettiset kantasolut hakeutuvat runsaslukuisesti juuri hydroksiapatiittipinnoitettuihin selluloosasieniin. Tämän hypoteesin mukaisesti hydroksiapatiittipinnoitettujen selluloosapalkkien läheisyydestä löydettiin suuria määriä kalsiumreseptoreja sisältäviä soluja. Jatkotutkimuksissa todettiin lisäksi, että hematopoieettiset kantasolut pystyivät sienissä erilaistumaan hemoglobiinia tuottaviksi soluiksi. Havaittujen punasolulinjan merkkiaineiden perusteella näyttäisikin siltä, että haavan paranemiskudoksessa tapahtuu paranemisen aikana ekstramedullaarista erytropoieesia. Nämä soluja ohjaavat vaikutukset saattavat olla hyödyllisiä vaikeasti paranevien haavojen hoidossa.

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.

Therapeutic Properties of Superoxide Dismutase 3 and Mesenchymal Stromal Cells in Peripheral Ischemia

The aim of this study was to characterize the cellular mechanisms leading to the beneficial effect of anti-oxidative gene therapy and pro-angiogenic stem cell therapy in acute peripheral ischemia. Post-ischemic events aim to re-establish tissue blood perfusion, to clear cellular debris, and to regenerate lost tissue by differentiation of satellite cells into myoblasts. Although leukocytes have an essential role in clearing cellular debris and promoting angiogenesis, they also contribute to tissue injury through excessive ROS production. First, we investigated the therapeutic properties of extracellular superoxide dismutase (SOD3) gene transfer. SOD3 was shown to reduce oxidative stress, to normalize glucose metabolism, and to enhance cell proliferation in the ischemic muscle. Analysis of the mitogenic Ras-Erk1/2 pathway showed SOD3 mediated induction offering a plausible explanation for enhanced cell proliferation. In addition, SOD3 reduced NF-κB activity by enhancing IκBα expression thus leading to reduced expression of inflammatory cytokines and adhesion molecules with consequent reduction in macrophage infiltration. Secondly, we sought to determine the fate and the effect of locally transplanted mesenchymal stem/stromal cells (MSCs) in acute ischemia. We showed that a vast majority of the transplanted cells are cleared from the injury site within 24 hours after local transplantation. Despite rapid clearance, transplantation was able to temporarily promote angiogenesis and cell proliferation in the muscle. Lack of graft-derived growth factor expression suggests other than secretory function to mediate this observed effect. In conclusion, both SOD3 and MSCs could be utilized to alleviate peripheral ischemia induced tissue injury. We have described a previously unidentified growth regulatory role for SOD3, and suggest a novel mechanism whereby transplanted MSCs enhance the reparative potential of the recipient tissue through physical contacts.

The relativity of evaluative sentences: disagreeing over disagreement

Evaluative sentences (moral judgments, expressions of taste, epistemic modals) are relative to the speaker's standards. Lately, a phenomenon has challenged the traditional explanation of this relativity: whenever two speakers disagree over them they contradict each other without being at fault. Hence, it is thought that the correction of the assertions involved must be relative to an unprivileged standard not necessarily the speaker's. I will claim instead that so far, neither this nor any other proposal has provided an explanation of the phenomenon. I will point out several problems presented by them and I will hint to how this phenomenon could be explained by making minor adjustments to our semantic theory.

Målarpoeten Ellen Thesleff : teknik och konstnärligt uttryck

The aim of this thesis has been to illustrate the multifaceted talent in Ellen Thesleff's (1869 - 1954) work with particular emphasis on her technique and artistic expression. Why did Ellen Thesleff work withso many techniques? How did the technique affect the expression and what characterizes it? It would also be of interest to gather some idea of Ellen Thesleff's position among other artists. The investigation covers a representative selection of about 60 pictures, using nine different techniques, primarily as oils, woodcuts and monumental painting. The pictures illustrate three periods of time, the natural (1890 - 1905), the colourful (1906 - 1927) and the free period (1928 -1950). I describe the pictures in regard to their conception and subject matter and scrutinize their formal creation. Thereafter, I investigate the painting technique and artistic expression of each picture and position it, where applicable, in relation to other art. Ellen Thesleff's artistic quality is discussed in relation to her techniques and expression. Thesleff consciously chooses different techniques for related subjects in order to vary the expression. The progressing evolution within individual techniques and a cross-fertilization between them has evidently contributed to raising her artistic quality. I have studied how the techniques influence expression and found it possible to identify certain characteristic styles during the three periods: first a natural painting technique which reminds one of both French realism, paintings reflecting the Nordic mood and atmosphere, and symbolism, ascetism and synthetism; later an expressive Thesleff colourism with brilliant over- and underpainting in contrasting colours and last a free decorative painting in lines, with symbolistic undertones. Most characteristic is the lyrical expression which seems to be a common theme throughout Thesleff's entire artistry. I have found that Ellen Thesleff in her works had herown personal style compared to her contemporaries. Despite deep knowledge of styles and techniques she continually creates art from her inner self and with her own personal brush signature.

Analysis on firm innovation boundaries

Innovation has been widely recognized as an important driver of firm competitiveness, and the firm’s internal research and development (R&D) activities are often considered to have a critical role in innovation activities. Internal R&D is, however, not the source of innovation as firms may tap into knowledge necessary for innovation also through various types of sourcing agreements or by collaborating with other organizations. The objective of this study is to analyze the way firms go about organizing efficiently their innovation boundaries. Within this context, the analysis is focused, firstly, on the relation between innovation boundaries and firm innovation performance and, secondly, on the factors explaining innovation boundary organization. The innovation literature recognizes that the sources of innovation depend on the nature of technology but does not offer a sufficient tool for analyzing innovation boundary options and their efficiency. Thus, this study suggests incorporating insights from transaction cost economics (TCE) complemented with dynamic governance costs and benefits into the analysis. The thesis consists of two parts. The first part introduces the background of the study, research objectives, an overview of the empirical studies, and the general conclusions of the study. The second part is formed of five publications. The overall results firstly indicate that although the relation between firm innovation boundary options is partly industry sector-specific, the firm level search strategies and knowledge transfer capabilities are important for innovation performance independently of the sector. Secondly, the results show that the attributes suggested by TCE alone do not offer a sufficient explanation of innovation boundary selection, especially under conditions of high levels of (radical) uncertainty. Based on the results, the dynamic governance cost and benefit framework complements the static TCE when firm innovation boundaries are scrutinized.

General terms and rigidity: another solution to the trivialization problem

In this paper I am concerned with the problem of applying the notion of rigidity to general terms. In Naming and Necessity, Kripke has clearly suggested that we should include some general terms among the rigid ones, namely, those common nouns semantically correlated with natural substances, species and phenomena, in general, natural kinds -'water', 'tiger', 'heat'- and some adjectives -'red', 'hot', 'loud'. However, the notion of rigidity has been defined for singular terms; after all, the notion that Kripke has provided us with is the notion of a rigid designator. But general terms do not designate single individuals: rather, they apply to many of them. In sum, the original concept of rigidity cannot be straightforwardly applied to general terms: it has to be somehow redefined in order to make it cover them. As is known, two main positions have been put forward to accomplish that task: the identity of designation conception, according to which a rigid general term is one that designates the same property or kind in all possible worlds, and the essentialist conception, which conceives of a rigid general term as an essentialist one, namely, a term that expresses an essential property of an object. My purpose in the present paper is to defend a particular version of the identity of designation conception: on the proposed approach, a rigid general term will be one that expresses the same property in all possible worlds and names the property it expresses. In my opinion, the position can be established on the basis of an inference to the best explanation of our intuitive interpretation and evaluation, relative to counterfactual circumstances, of statements containing different kinds of general terms, which is strictly analogous to our intuitive interpretation and evaluation, relative to such circumstances, of statements containing different kinds of singular ones. I will argue that it is possible to offer a new solution to the trivialization problem that is thought to threaten all versions of the identity of designation conception of rigidity. Finally, I will also sketch a solution to the so-called 'over-generalization and under-generalization problems', both closely related to the above-mentioned one.

A SECOND OPINION ON RELATIVE TRUTH

In 'An undermining diagnosis of relativism about truth', Horwich claims that the notion of relative truth is either explanatorily sterile or explanatorily superfluous. In the present paper, I argue that Horwich's explanatory demands set the bar unwarrantedly high: given the philosophical import of the theorems of a truth-theoretic semantic theory, Horwich's proposed explananda, what he calls acceptance facts, are too indirect for us to expect a complete explanation of them in terms of the deliverances of a theory of meaning based on the notion of relative truth. And, to the extent that there might be such an explanation in certain cases, there is no reason to expect relative truth to play an essential, ineliminable role, nor to endorse the claim that it should play such a role in order to be a theoretically useful notion.

Kaukojäähdytyksen potentiaali ja kannattavuus Oulun keskustan alueella

Diplomityö on tehty Oulun Energian kaukolämpöosastolle. Työn tavoitteena oli selvittää kaukojäähdytyksen asiakaspotentiaali Oulun keskustan alueella sekä tehdä esiselvitys kaukojäähdytysinvestoinnin kannattavuudesta. Potentiaalin kartoituksessa otettiin huomioon sekä nykyiset rakennukset että lähitulevaisuuden lisärakentaminen. Jäähdytyskuormaksi Oulun keskustassa saatiin 28 MW, josta suurin osa on liiketiloja, toimistorakennuksia sekä hotelleja. Investoinnin kannattavuutta tutkittiin perinteisillä investointilaskennan menetelmillä. Kustannusarvio perustuu vapaajäähdytykseen ja absorptiojäähdytykseen ja tuotantolaitoksen sijoittamiseen kalliotiloihin. Tuottojen arviointia varten määriteltiin alustava kaukojäähdytystariffi sekä kolme erilaista kasvumallia. Tulosten perusteella investointi vaikuttaisi kannattamattomalta. Pääsyynä kannattamattomuuteen on kallis alkuinvestointi, jossa etenkin louhinnan osuus on merkittävä. Toisena syynä kannattamattomuuteen voidaan pitää potentiaalisten kaukojäähdytykseen liitettävien rakennusten melko pientä kokoa Oulun keskustassa.

Momentum-anomalia ja siihen perustuvat sijoitusstrategiat Yhdysvaltojen osakemarkkinoilla

Tutkielmassa lähestytään osakemarkkinoilla havaittua poikkeavuutta, momentum-anomaliaa, sekä sen ilmenemistä ja selittyvyyttä Yhdysvaltojen osakemarkkinoiden olosuhteissa. Lisäksi tutkielma sisältää lyhyen katsauksen kansainvälisesti ilmenevään momentumiin kuin myös sen muodostumiseen vaikuttaviin tekijöihin. Työn tutkimusongelmana on, selittyykö Yhdysvaltojen osakemarkkinoilla ilmenevä momentum-anomalia selkeämmin behaviorististen vai makrotaloudellisten riskitekijöiden muodostamien mallien avulla. Kuten aiempi tutkimus on havainnut, myös tässä tutkielmassa oletuksena on, että behavioristis-perusteiset tekijät omaavat suuremman selitysvoiman, kuin makrotaloudellisten riskitekijöiden -perusteiset mallit. Yksittäisiin tekijöihin keskittymisen ohella on tarkoitus havainnoida momentum-anomalian ilmentymisen riippuvuus markkinasuhdanteista, jolloin syntyviä momentumin tuottoja tarkastellaan sekä korkea-, että matalasuhdannemarkkinoiden olosuhteissa.

Cyanobacteria from the Baltic Sea and Finnish lakes as an energy source and modulators of bioenergetic pathways

Cyanobacteria are a diverse group of oxygenic photosynthetic bacteria that inhabit in a wide range of environments. They are versatile and multifaceted organisms with great possibilities for different biotechnological applications. For example, cyanobacteria produce molecular hydrogen (H2), which is one of the most important alternatives for clean and sustainable energy. Apart from being beneficial, cyanobacteria also possess harmful characteristics and may become a source of threat to human health and other living organisms, as they are able to form surface blooms that are producing a variety of toxic or bioactive compounds. The University of Helsinki Culture Collection (UHCC) maintains around 1,000 cyanobacterial strains representing a large number of genera and species isolated from the Baltic Sea and Finnish lakes. The culture collection covers different life forms such as unicellular and filamentous, N2-fixing and non-N2-fixing strains, and planktonic and benthic cyanobacteria. In this thesis, the UHCC has been screened to identify potential strains for sustainable biohydrogen production and also for strains that produce compounds modifying the bioenergetic pathways of other cyanobacteria or terrestrial plants. Among the 400 cyanobacterial strains screened so far, ten were identified as high H2-producing strains. The enzyme systems involved in H2 metabolism of cyanobacteria were analyzed using the Southern hybridization approach. This revealed the presence of the enzyme nitrogenase in all strains tested, while none of them are likely to have contained alternative nitrogenases. All the strains tested, except for two Calothrix strains, XSPORK 36C and XSPORK 11A, were suggested to contain both uptake and bidirectional hydrogenases. Moreover, 55 methanol extracts of various cyanobacterial strains were screened to identify potent bioactive compounds affecting the photosynthetic apparatus of the model cyanobacterium, Synechocystis PCC 6803. The extract from Nostoc XPORK 14A was the only one that modified the photosynthetic machinery and dark respiration. The compound responsible for this effect was identified, purified, and named M22. M22 demonstrated a dual-action mechanism: production of reactive oxygen species (ROS) under illumination and an unknown mechanism that also prevailed in the dark. During summer, the Baltic Sea is occupied by toxic blooms of Nodularia spumigena (hereafter referred to as N. spumigena), which produces a hepatotoxin called nodularin. Long-term exposure of the terrestrial plant spinach to nodularin was studied. Such treatment resulted in inhibition of growth and chlorosis of the leaves. Moreover, the activity and amount of mitochondrial electron transfer complexes increased in the leaves exposed to nodularin-containing extract, indicating upregulation of respiratory reactions, whereas no marked changes were detected in the structure or function of the photosynthetic machinery. Nodularin-exposed plants suffered from oxidative stress, evidenced by oxidative modifications of various proteins. Plants initiated strategies to combat the stress by increasing the levels of alpha-tocopherol, mitochondrial alternative oxidase (AOX), and mitochondrial ascorbate peroxidase (mAPX).