Electrocatalytic oxidation of methanol by the [Ru3O(OAc)6(py)2(CH3OH)]3+cluster: improving the metal-ligand electron transfer by accessing the higher oxidation states of a multicentered system

The [Ru3O(Ac)6(py)2(CH3OH)]+ cluster provides an effective electrocatalytic species for the oxidation of methanol under mild conditions. This complex exhibits characteristic electrochemical waves at -1.02, 0.15 and 1.18 V, associated with the Ru3III,II,II/Ru3III,III,II/Ru 3III,III,III /Ru3IV,III,III successive redox couples, respectively. Above 1.7 V, formation of two RuIV centers enhances the 2-electron oxidation of the methanol ligand yielding formaldehyde, in agreement with the theoretical evolution of the HOMO levels as a function of the oxidation states. This work illustrates an important strategy to improve the efficiency of the oxidation catalysis, by using a multicentered redox catalyst and accessing its multiple higher oxidation states.

A teoria de pearson para a disciplina de química orgânica: um exercício prático e teórico aplicado em sala de aula

We report a didactic experience in teaching Pearson's theory (HSAB) to graduate students in organic chemistry. This approach was based on teaching students how to use computer programs to calculate frontier orbitals (HOMO-LUMO). The suggested level of calculation was a semi-empiric PM3, proving to be efficient for obtaining robust and fast numerical results that can be performed easily in the classroom. We described a practical computational exercise and asked students to compare these numerical data with qualitative analysis using valence bond theory. A comprehensive solution of this exercise is presented, aiming to support teachers in their lessons.

Synthesis, characterization and computational studies of (E)-2-{[(2-aminopyridin-3-yl)imino]-methyl}-4,6-di-tert-butylphenol

(E)-2-{[(2-Aminopyridin-3-yl)imino]-methyl}-4,6-di-tert-butyl-phenol ( 3: ), a ligand containing an intramolecular hydrogen bond, was prepared according to a previous literature report, with modifications, and was characterized by UV-vis, FTIR, ¹H-NMR, 13C-NMR, HHCOSY, TOCSY and cyclic voltammetry. Computational analyses at the level of DFT and TD-DFT were performed to study its electronic and molecular structures. The results of these analyses elucidated the behaviors of the UV-vis and electrochemical data. Analysis of the transitions in the computed spectrum showed that the most important band is primarily composed of a HOMO→LUMO transition, designated as an intraligand (IL) charge transfer.

Carcinogenicidade do carbendazim e seus metabólitos

The carcinogenic potential of carbendazim and its metabolites was analyzed using statistical treatment of electronic parameters obtained from DFT/ 6-311++G(d,p) and AM1 calculations. The carcinogen-DNA interaction is described in the framework of the theory of unsynchronized resonance of covalent bond as a process of electron transfer involving the HOMO and LUMO frontier orbitals. Through a Principal Component Analysis (PCA) of the electron affinity, carcinogen-DNA interaction energy, electrostatic attraction and cell membrane permeability (dipole moment m and partition coefficient LogP) evidence was obtained showing carbendazim displays carcinogenic activity. For the metabolites of carbendazim, no evidence was found in the literature of their carcinogenic activities. However, the electronic parameters for these metabolites exhibited similarity to known carcinogens, thereby showing the importance of the results obtained in this study for a policy based on the precautionary principle.

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.

L'ontologie chez Heidegger et chez Lukacs - Phénoménologie et dialectique

L'auteur de ce texte a abordé auparavant à plusieurs reprises le sujet d'une confrontation entre les pensées de Heidegger et de Lukacs. Il est parti de l'idée qu'ils existent des motifs communs entre les deux pensées, par exemple le thème de l'aliénation et celui de la réification, et il a publié deux articles dans ce sens. Le texte publié ici poursuit un objectif plus ambitieux, car il se propose de remonter aux fondements ontologiques des deux pensées et confronter Heidegger et Lukacs à partir de leur opposition sur pluseurs questions philosophiques cruciales : l'autonomie ontologique du monde extérieur, la définition du concept de "monde", la "subjectivité du sujet" et la humanitas de l'homo humanus, la critique lukacsienne du concept heideggérien d'"être-jeté..." (Geworfenheit),la problématique de la finitude et de l'infini,etc. La thèse centrale de l'article est l'occultation par Heidegger du travail comme "phénomène originaire" de l'existence humaine et sa substitution par une catégorie affective: le "Souci" (die Sorge), tandis que Lukacs a construit son ontologie de l'être social, en suivant Hegel et Marx, sur l'idée du travail comme pivot de l'existence humaine. La partie finale du texte désigne plusieurs motifs de la pensée heideggérienne (la critique de la pensée sécurisante, par ex.) qui préfigurent l'adhésion du philosophe à l'extrême droite de l'époque, ce qui confirme la thèse de Lukacs formulée dans son livre La Destruction de la Raison sur le caractère "pré-fasciste" de certaines orientations de la philosophie heideggérienne à l'époque qui asuccédé à son livre fameux Être et Temps.

Pluralité et fluidité antinormatives : étude sur les transgressions sexuelles dans l’oeuvre romanesque de Marguerite Yourcenar

Avhandlingen är en studie i kön, genus och sexualitet i den franska författarinnan Marguerite Yourcenars romaner. Undersökningen utgår från ett queer-teoretiskt perspektiv och har som syfte att belysa de olika sätt på vilka Yourcenars texter uttrycker ett ifrågasättande av och ett överskridande av normer beträffande kön, manlighet och kvinnlighet, samt sexuella kategorier. Det tudelade könssystemet (man/kvinna) och motsättningen mellan heterosexualitet och homosexualitet ses som förenklade sociala konstruktioner som inte motsvarar den mångfasetterade verklighet som avbildas i texterna. Mångfald, flyktighet och gränsöverskridande är nyckelord i undersökningen. I avhandlingen granskas snart när alla Yourcenars romaner samt en novell i form av separata läsningar, för att ge en så heltäckande bild som möjligt av hur problematiken behandlas i hennes produktion. Således belyses särarten hos varje verk och det är även möjligt att uppmärksamma den utveckling som skett under karriärens gång. Kön och sexualitet diskuteras separat i enlighet med Gayle Rubins och Eve Sedgwicks tes att sexualitetsforskning och genusstudier inte bör sammanblandas: sexualitet är ett så komplext fenomen att kön och genus är otillräckliga analysverktyg för en seriös och djuplodande diskussion. Genom att lyfta fram olika exempel på figurer i Yourcenars romaner som implicit eller explicit tar avstånd ifrån en klar indelning i män och kvinnor, respektive manlighet och kvinnlighet, påvisas att tanken att det existerar två olika biologiska kön systematiskt tillbakavisas. Diskussionen om sexualitetstemat koncentrerar sig på förhållandet mellan homo-och heterosexualitet, men betonar även hur temat anknyter till andra centrala teman, såsom religion och ras. Bilden av homosexualitet ändrar från en text till en annan, vilket illusterar att en skarp motsättning mellan homo- och heterosexualitet är ohållbar.

Heteronormatiivisuus ja sukupuoli

Kirjallisuusarvostelu

Comparative anatomy of the thigh nerves of Cebus libidinosus (Rylands et al., 2000)

Non-human primates have constituted an important group among animals subjected to various studies. Ethological, evolutionary and paleontological studies have revealed changes in anatomical structures linked to the evolution of primates, considered in studies on the comparative anatomy between Cebus libidinosus and other neotropical monkeys or those from the Old World, and the detailed knowledge on their anatomy may represent an important factor for their preservation and protection when the animals are brought to veterinary clinics after accidents or illnesses. In terms of veterinary importance, sometimes these animals arrive in the veterinary medical clinics after accidents, needing surgery or clinical treatment, but the little data available on anatomy has impaired the correct proceedings. The main justification for studies on C. libidinosus, is due to little information about the anatomy related to C. libidinosus in Brazilian and worldwide scientific literature. In this study, the distribution, enervation and path of the femoral and sciatic nerves of the pelvic limb (thigh) of C. libidinosus were studied and these results were compared with literature on the anatomy of humans, chimpanzees and baboons. In general, the enervation model of the four primates is identical, but in specific terms, the differences in enervations indicate evolution convergence closer to the branch of baboons in the evolutionary tree, and these data corroborate other comparative studies in relation to the same primates to vessels, muscles and nerves. In conclusion, the nerve organization in the thigh of C. libidinosus is identical to baboon, chimpanzee and homo, but more similar to baboon. The specific differences found indicate an ancient phylogenic origin to C. libidinosus and baboons (data corroborated by other studies).

Non-profit maximising organisations and the impact of privatisation, liberalisation, and public-sector reform

I denna avhandling analyserar jag både offentliga och privata företag och organisationer, inklusive universitet, särskilt när det existerar potentiell inre motivation. Jag behandlar både industriell produktion, inklusive infrastruktursektorer med vertikala relationer, och tjänstesektorn. Man tänker sig att ägandet kan påverka kostnadseffektiviteten dels genom olika storlek hos lönetillägg och andra förmåner för de anställda (eng. Internal Rent Capture), och dels via asymmetrisk information. Jag frågar dessutom om det finns andra faktorer än ägande och konkurrens som kan påverka prestandan hos kommersiella företag och ideella organisationer. Dessa frågeställningar aktualiseras av pågående reformer inom den offentliga sektorn, särskilt i samband med den så kallade nya offentliga förvaltningen (eng. New Public Management). Jag analyserar reformernas inverkan på hur bra en organisation fungerar och på den sociala välfärden. Analysen i denna avhandling är teoretisk, men resultaten är relaterade också till den empiriska litteraturen. Avhandlingen är uppdelad i del I och II. I del I sammanfattar jag avhandlingen och sätter den i ett sammanhang, medan del II består av fem redan publicerade essäer. De två första (I–II) är mera traditionella, i och med att de baserar sig på homo economicus (eng. the economic man), utan att beakta den inre motivationen. I essä I (publicerad 2008) bedömer vi fördelar och nackdelar av privatisering och avreglering innanför en sådan ram, men med en betoning också på icke återvinningsbara fasta kostnader och vertikala relationer. I essä II (publicerad 2012) fokuserar vi oss på vertikal separation, och konkurrensutsättning och privatisering i nätverksindustrier. I essäerna III–V vidgas perspektivet genom att införa potentiell inre motivation i en agentmodell. Analysen i essä III (publicerad 2014) tillämpas på offentligt ägande och privatisering. I essäerna IV och V (publicerade 2009 respektive 2013) utvidgas analysen till att även gälla kreativa branscher, särskilt arbete inom universiteten, där den inre motivationen hos de anställda kan tänkas vara avgörande. I dessa essäer tillämpas en analys som inbegriper ett intra-personellt spel inom ramen för en agentmodell med potentiell inre motivation. Vi analyserar sålunda avvägningen mellan ekonomiska incitament och inre motivation.

Gap junctions in cells of the immune system: structure, regulation and possible functional roles

Gap junction channels are sites of cytoplasmic communication between contacting cells. In vertebrates, they consist of protein subunits denoted connexins (Cxs) which are encoded by a gene family. According to their Cx composition, gap junction channels show different gating and permeability properties that define which ions and small molecules permeate them. Differences in Cx primary sequences suggest that channels composed of different Cxs are regulated differentially by intracellular pathways under specific physiological conditions. Functional roles of gap junction channels could be defined by the relative importance of permeant substances, resulting in coordination of electrical and/or metabolic cellular responses. Cells of the native and specific immune systems establish transient homo- and heterocellular contacts at various steps of the immune response. Morphological and functional studies reported during the last three decades have revealed that many intercellular contacts between cells in the immune response present gap junctions or "gap junction-like" structures. Partial characterization of the molecular composition of some of these plasma membrane structures and regulatory mechanisms that control them have been published recently. Studies designed to elucidate their physiological roles suggest that they might permit coordination of cellular events which favor the effective and timely response of the immune system.

Is pancreas development abnormal in the non-obese diabetic mouse, a spontaneous model of type I diabetes?

Despite extensive genetic and immunological research, the complex etiology and pathogenesis of type I diabetes remains unresolved. During the last few years, our attention has been focused on factors such as abnormalities of islet function and/or microenvironment, that could interact with immune partners in the spontaneous model of the disease, the non-obese diabetic (NOD) mouse. Intriguingly, the first anomalies that we noted in NOD mice, compared to control strains, are already present at birth and consist of 1) higher numbers of paradoxically hyperactive ß cells, assessed by in situ preproinsulin II expression; 2) high percentages of immature islets, representing islet neogenesis related to neonatal ß-cell hyperactivity and suggestive of in utero ß-cell stimulation; 3) elevated levels of some types of antigen-presenting cells and FasL+ cells, and 4) abnormalities of extracellular matrix (ECM) protein expression. However, the colocalization in all control mouse strains studied of fibroblast-like cells (anti-TR-7 labeling), some ECM proteins (particularly, fibronectin and collagen I), antigen-presenting cells and a few FasL+ cells at the periphery of islets undergoing neogenesis suggests that remodeling phenomena that normally take place during postnatal pancreas development could be disturbed in NOD mice. These data show that from birth onwards there is an intricate relationship between endocrine and immune events in the NOD mouse. They also suggest that tissue-specific autoimmune reactions could arise from developmental phenomena taking place during fetal life in which ECM-immune cell interaction(s) may play a key role.

Ureases display biological effects independent of enzymatic activity: Is there a connection to diseases caused by urease-producing bacteria?

Ureases are enzymes from plants, fungi and bacteria that catalyze the hydrolysis of urea to form ammonia and carbon dioxide. While fungal and plant ureases are homo-oligomers of 90-kDa subunits, bacterial ureases are multimers of two or three subunit complexes. We showed that some isoforms of jack bean urease, canatoxin and the classical urease, bind to glycoconjugates and induce platelet aggregation. Canatoxin also promotes release of histamine from mast cells, insulin from pancreatic cells and neurotransmitters from brain synaptosomes. In vivo it induces rat paw edema and neutrophil chemotaxis. These effects are independent of ureolytic activity and require activation of eicosanoid metabolism and calcium channels. Helicobacter pylori, a Gram-negative bacterium that colonizes the human stomach mucosa, causes gastric ulcers and cancer by a mechanism that is not understood. H. pylori produces factors that damage gastric epithelial cells, such as the vacuolating cytotoxin VacA, the cytotoxin-associated protein CagA, and a urease (up to 10% of bacterial protein) that neutralizes the acidic medium permitting its survival in the stomach. H. pylori whole cells or extracts of its water-soluble proteins promote inflammation, activate neutrophils and induce the release of cytokines. In this paper we review data from the literature suggesting that H. pylori urease displays many of the biological activities observed for jack bean ureases and show that bacterial ureases have a secretagogue effect modulated by eicosanoid metabolites through lipoxygenase pathways. These findings could be relevant to the elucidation of the role of urease in the pathogenesis of the gastrointestinal disease caused by H. pylori.

Kireää pintaa ja ammattitaitoisia kokeita. Konteksti, frekvenssi ja fonologinen läpinäkyvyys suomen kielen homonyymisten sanamuotojen tulkinnassa

Tutkimuksessa selvitellään kirjallisen testin avulla kontekstin, frekvenssin ja fonologisen läpinäkyvyyden vaikutusta suomen kielen homonyymisten sananmuotojen (esim. kokeista, pinnassa, suojaisin) tulkintaan. Testi pohjautuu Klaus Laalon (1990) homo-nyymisten sananmuotojen luokitukseen ja rakentuu perusmuotojen nimeämisen varaan. Homonyymiset sananmuodot (yht. 36 muotoa) esiintyvät joko kontekstissa tai kontekstitta, ja tehtävänannossa joko on tai ei ole viitattu muotojen monitulkintaisuuteen. Kontekstit ovat lisäksi joko rajaavia (sallivat vain yhden tulkinnan) tai neutraaleja (mahdollistavat useamman tulkinnan). Testiin on osallistunut yhteensä 57 yläkoululaista ja lukiolaista (50 suomenkielistä ja 7 S2-oppijaa). Tutkimuksessa selvitetään, vaikuttavatko konteksti, frekvenssi ja fonologinen läpinäkyvyys siihen, missä määrin homonyymisten sananmuotojen eri merkitykset oivalletaan ja millä perustein homonyymisten sananmuotojen tulkinta määräytyy silloin, kun vaihtoehtoisista merkityksistä oivalletaan vain jokin. Erityisen huomion kohteena on homonyymien tulkinta rajaavassa kontekstissa: ohjaako konteksti automaattisesti oikeaan tulkintaan, ja jäävätkö kontekstiin sopimattomat merkitykset huomaamatta (vrt. Laalo 1982: 7; 1990: 12), vai aktivoituvatko merkitykset kattavasti? Kysymyksenasettelu on psykolingvistinen, ja työssä myös Laalon (1982: 7; 1990: 12) näkemystä suhteutetaan homonyymien prosessoinnista tehtyyn tutkimukseen. Tulosten perusteella homonyymisten sananmuotojen monitulkintaisuus oivalletaan parhaiten silloin, kun muodot esiintyvät ilman kontekstia ja tehtävänanto ohjaa vaihtoehtoisten merkitysten pohdintaan; muulloin niiden monitulkintaisuus jää pitkälti huomaamatta – jopa silloin, kun monitulkintaisuudella leikitellään. Monitulkintaisuuden havaitseminen ei myöskään riippunut frekvenssistä eikä läpinäkyvyydestä, jotka kuitenkin vaikuttivat siihen, mitä perusmuotoa vain yhden tulkinnan oivaltaneet informantit suosivat. Rajaavassa kontekstissa homonyymiset sananmuodot tulkittiin usein kontekstinvastaisesti. Erityisen paljon virhetulkintoja esiintyi S2-oppijoilla ja yläkoululaisilla, ja ne kasautuivat konteksteihin, joissa kontekstuaalisesti oikea tulkinta vastasi homonyymisen sananmuodon harvinaisempaa merkitystä. Tulkinnan ratkaisi siis frekvenssi, eivät kontekstuaaliset vihjeet. Laalon (1982: 7; 1990: 12) hypoteesin voi kuitenkin katsoa toteutuvan niissä rajaavissa konteksteissa, joissa kontekstinmukainen tulkinta vastasi homonyymisen sananmuodon yleisempää merkitystä.

De anima in genere (1652)

Invokaatio: Sun Theo.