Estudo do comportamento fotocrómico de um naftopirano: uma experiência simples ilustrativa do fotocromismo

An easy experiment on the synthesis of 3,3-diphenyl-3H-naphtho[2,1-b]pyran and characterization of its photochromic behaviour is reported. Upon irradiation of an uncoloured toluene solution of 3,3-diphenyl-3H-naphtho[2,1-b]pyran with near UV light, an intense yellow colouration is produced due to the formation of two coloured open forms. When the irradiation source is removed the coloured open forms return to the uncoloured state. The analysis of the absorbance decay with time allows the determination of the discoloration rate constants of each open form. The reversibility of the photochromic phenomenon, well demonstrated by the exposure of the solution to sunlight for a few seconds, is particularly attractive to the students.

Fe3+-SELECTIVE ENHANCED FLUORESCENCE PROBE BASED ON A RHODAMINE DERIVATIVE

A novel Fe3+-selective and turn-on fluorescent probe 1 incorporating a rhodamine fluorophore and quinoline subunit was synthesized. Probe 1 displayed high selectivity for Fe3+ in CH3CN–H2O (95:5 v/v) in the presence of other relevant metal cations. Interaction with Fe3+ in 1:1 stoichiometry could trigger a significant fluorescence enhancement due to the formation of the ring-open form. The fluorescent response images were investigated by a novel Euclidean distance method based on red, green, and blue values. A linear relationship was observed between fluorescence intensity changes and Fe3+ concentrations from 7.3 × 10−7 to 3.6 × 10−5 mol L−1.

In vitro fermentation of a red wine extract by human gut microbiota: changes in microbial groups and formation of phenolic metabolites

An in vitro batch culture fermentation experiment was conducted with fecal inocula from three healthy volunteers in the presence and absence of a red wine extract. Changes in main bacterial groups were determined by FISH during a 48 h fermentation period. The catabolism of main flavonoids (i.e., flavan-3-ols and anthocyanins) and the formation of a wide a range of phenolic microbial metabolites were determined by a targeted UPLC-PAD-ESI-TQ MS method. Statistical analysis revealed that catechol/pyrocatechol, as well as 4-hydroxy-5-(phenyl)-valeric, 3- and 4-hydroxyphenylacetic, phenylacetic, phenylpropionic, and benzoic acids, showed the greatest increases in concentration during fermentation, whereas 5-(3′-hydroxyphenyl)-γ-valerolactone, its open form 4-hydroxy-5-(3′-hydroxyphenyl)-valeric acid, and 3,4-dihydroxyphenylacetic acid represented the largest interindividual variations in the catabolism of red wine polyphenols. Despite these changes, microbial catabolism did not produce significant changes in the main bacterial groups detected, although a slight inhibition of the Clostridium histolyticum group was observed.

Modelling the effects of gravity waves on stratocumulus clouds observed during VOCALS-UK

During the VOCALS campaign spaceborne satellite observations showed that travelling gravity wave packets, generated by geostrophic adjustment, resulted in perturbations to marine boundary layer (MBL) clouds over the south-east Pacific Ocean (SEP). Often, these perturbations were reversible in that passage of the wave resulted in the clouds becoming brighter (in the wave crest), then darker (in the wave trough) and subsequently recovering their properties after the passage of the wave. However, occasionally the wave packets triggered irreversible changes to the clouds, which transformed from closed mesoscale cellular convection to open form. In this paper we use large eddy simulation (LES) to examine the physical mechanisms that cause this transition. Specifically, we examine whether the clearing of the cloud is due to (i) the wave causing additional cloud-top entrainment of warm, dry air or (ii) whether the additional condensation of liquid water onto the existing drops and the subsequent formation of drizzle are the important mechanisms. We find that, although the wave does cause additional drizzle formation, this is not the reason for the persistent clearing of the cloud; rather it is the additional entrainment of warm, dry air into the cloud followed by a reduction in longwave cooling, although this only has a significant effect when the cloud is starting to decouple from the boundary layer. The result in this case is a change from a stratocumulus to a more patchy cloud regime. For the simulations presented here, cloud condensation nuclei (CCN) scavenging did not play an important role in the clearing of the cloud. The results have implications for understanding transitions between the different cellular regimes in marine boundary layer (MBL) clouds.

Asymmetric oxidation of vinyl- and ethynyl terthiophene ligands in triruthenium complexes

A series of ruthenium(II) complexes [{RuCl(CO)(PMe3)3(–CHvCH–)}nX], 1a–1c (1a: n = 3, X = 3,3’’- dimethyl-2,2’:3’,2’’-terthiophene; 1b: n = 2, X = 2,2’-bithiophene; 1c: n = 2, X = 2,3-bis(3-methylthiophen- 2-yl)benzothiophene) and [{Cp*(dppe)2Ru(–CuC–)}3X], 1d (X = 3,3’’-dimethyl-2,2’:3’,2’’- terthiophene), were prepared and characterized by 1H, 13C and 31P NMR. Their redox, spectroscopic and bonding properties were studied with a range of spectro-electrochemical methods in combination with density functional theory calculations. The first two anodic steps observed for 1a and 1d are largely localized on the lateral frameworks of the molecular triangle, the direct conjugation between them being precluded due to the photostable open form of the dithienyl ethene moiety. The third anodic step is then mainly localized on the centerpiece of the triangular structure, affecting both bithiophene laterals. The experimental IR and UV-vis-NIR spectroelectrochemical data and, largely, also DFT calculations account for this explanation, being further supported by direct comparison with the anodic behavior of reference diruthenium complexes 1b and 1c.

Modulation of the activity and selectivity of the immobilized lipases by surfactants and solvents

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

"Narrativa di frontiera". Fenomenologia di una forma aperta.

«Fiction of frontier». Phenomenology of an open form/voice. Francesco Giustini’s PhD dissertation fits into a genre of research usually neglected by the literary criticism which nevertheless is arousing much interest in recent years: the relationship between Literature and Space. In this context, the specific issue of his work consists in the category of the Frontier including its several implications for the XX century fiction. The preliminary step, at the beginning of the first section of the dissertation, is a semantic analysis: with precision, Giustini describes the meaning of the word “frontier” here declined in a multiplicity of cultural, political and geographical contexts, starting from the American frontier of the pioneers who headed for the West, to the exotic frontiers of the world, with whose the imperialistic colonization has come into contact; from the semi-uninhabited areas like deserts, highlands and virgin forests, to the ethnic frontiers between Indian and white people in South America, since the internal frontiers of the Countries like those ones between the District and the Capital City, the Centre and the Outskirts. In the next step, Giustini wants to focus on a real “ myth of the frontier”, able to nourish cultural and literary imagination. Indeed, the literature has told and chosen the frontier as the scenery for many stories; especially in the 20th Century it made the frontier a problematic space in the light of events and changes that have transformed the perception of space and our relationship with it. Therefore, the dissertation proposes a critical category, it traces the hallmarks of a specific literary phenomenon defined “ Fiction of the frontier” ,present in many literary traditions during the 20th Century. The term “Fiction” (not “Literature” or “Poetics”) does not define a genre but rather a “procedure”, focusing on a constant issue pointed out from the texts examined in this work : the strong call to the act of narration and to its oral traditions. The “Fiction of the Frontier” is perceived as an approach to the world, a way of watching and feeling the objects, an emotion that is lived and told through the story- a story where the narrator ,through his body and his voice, takes the rule of the witness. The following parts, that have an analytic style, are constructed on the basis of this theoretical and methodological reflection. The second section gives a wide range of examples into we can find the figure and the myth of the frontier through the textual analysis which range over several literary traditions. Starting from monographic chapters (Garcia Marquez, Callado, McCarthy), to the comparative reading of couples of texts (Calvino and Verga Llosa, Buzzati and Coetzee, Arguedas and Rulfo). The selection of texts is introduced so as to underline a particular aspect or a form of the frontier at every reading. This section is articulated into thematic voices which recall some actions that can be taken into the ambiguous and liminal space of the frontier (to communicate, to wait, to “trans-culturate”, to imagine, to live in, to not-live in). In this phenomenology, the frontier comes to the light as a physical and concrete element or as a cultural, imaginary, linguistic, ethnic and existential category. In the end, the third section is centered on a more defined and elaborated analysis of two authors, considered as fundamental for the comprehension of the “Fiction of the frontier”: Joseph Conrad and João Guimarães Rosa. Even if they are very different, being part of unlike literary traditions, these two authors show many connections which are pointed by the comparative analysis. Maybe Conrad is the first author that understand the feeling of the frontier , freeing himself from the adventure romance and from the exotic nineteenthcentury tradition. João Guimarães Rosa, in his turn, is the great narrator of Brazilian and South American frontier, he is the man of sertão and of endless spaces of the Centre of Brazil. His production is strongly linked to that one belonged to the author of Heart of Darkness.

Aggressive Behaviour of Different Social and Demographic Groups in Post-Totalitarian Society

The project looked at aggressiveness in different age and social groups of modern post-totalitarian society, beginning with the hypotheses that the greatest risk groups are teenagers and the unemployed, and that there is a link between aggression and the level of meaningfulness of life. The groups studied comprised about 200 persons from urban areas of eastern Ukraine, including schoolchildren, students, white collar workers, self-employed persons, the unemployed and pensioners. Workers in industry were not included as this group has virtually disappeared in Ukraine at present since most enterprises have ceased to work and most workers have moved into the groups of the unemployed or self-employed. Participants were divided into age groups of 13-14, 16-17, 18-22, 24-45, 46-60 and over 60, with each group including approximately equal number of men and women. Research methods included Buss-Darky techniques, the "hand test" (E. Wagner), the "non-existent animal" technique, a Rozenzweig picture frustration study, purpose-in-life tests and an interview. The Buss-Darky test showed that schoolchildren have the highest level of aggression, followed by students. These groups have high indexes in virtually all types of aggression, including its open form. The self-employed have relatively lower indexes, although they are more likely to manifest it openly, while such open manifestations are less likely among white-collar workers, pensioners and the unemployed. The least aggressive were the unemployed and pensioners, although the latter had a relatively high level of hostility. In terms of age, aggression was shown to decrease with age, which Ms. Ivanova attributes to the still imperfect control mechanisms of teenagers and their less mature personalities. Among the younger groups girls showed a slightly higher level of aggression, although this situation was reversed among older people. The risk groups inclined to manifest open forms of aggressiveness can therefore be seen to be teenagers and students. Other tests used show aggressiveness as a feature of the current state, rather than as an inherent feature and the results obtained were somewhat different. In the interviews, all adults referred to the increased aggressiveness in society and most stated that they themselves had become more aggressive and bad-tempered. The ability of individuals to adapt to their social environment was also investigated and schoolchildren turned out to have the lowest adaptation index and the unemployed the highest. MS. Ivanova attributes that latter, rather surprising, result to the fact that the constant frustrations facing the unemployed force them to actively seek ways and means of adapting in order to survive. The final aspect considered was the possible connection between human aggressiveness and the meaningfulness of life. Here the groups with the most meaningful lives were the self-employed and pensioners. The latter result, again rather surprising, was attributed to the desire of people who have already lived the greater part of their lives to place more weight on what they have already done, in order to prove to themselves that they have not lived in vain. The hypothesis that aggressiveness is conversely related to the meaningfulness of life was only partially confirmed. In the two extreme cases (schoolchildren and pensioners) this was indeed the case, but the remaining groups did not show any such connection. From the data obtained, Ms. Ivanova concluded that life in modern post-totalitarian society does indeed foster a rise in people's aggressiveness, and this was supported by the fact that indexes of aggressiveness proved to be higher than the norm. Her original hypothesis as to the groups in society most at risk from open aggression confirmed in the case of teenagers but not of the unemployed, who had relatively low aggressiveness indexes and the highest degree of adaptation.

The debate on human automatism in mid-Victorian England

During the 1830s, Marshall Hall carried out innumerable experiments on a great variety of animals to establish the concept of a ‘reflex arc’. In France F.L.Goltz showed that decerebrate frogs were still capable of complex behaviours. Thomas Laycock in England and Ivan Sechenov in Russia sought to apply the reflex idea to the brain. This paper follows the debate in the periodical literature of mid-Victorian England and discusses the contributions of WB Carpenter, Herbert Spencer, TH Huxley, W Clifford and others. The previous outing of this issue in the post-Cartesian seventeenth century had been largely suppressed by ecclesiastical authority. In the nineteenth century ecclesiastical power had waned, at least in England, and the debate could take a more open form. As neurophysiology and behavioural science developed, with the widespread acceptance of Darwinian evolution, it became more and more difficult to deny that brain and mind were part of the natural world and subject to the usual laws of cause and effect. This, of course, had powerful implications for the human self-image and for jurisprudence. These implications are still with us and the work of neurophysiologists such as Benjamin Libet have only reinforced them. Should humans be regarded as ‘automata’ and, if so, what becomes of ‘free will’, ‘responsibility’, and the rule of law? The Victorian debate is still useful and relevant.

As vicissitudes do espaço urbano moderno ou o menino e a água do banho

Tese de Doutoramento em Arquitetura, com a especialização em Teoria e Prática do Projecto, apresentada na Faculdade de Arquitetura da Universidade de Lisboa, para obtenção do grau de Doutor.

Synthesis and Characterization of Photochromic Copolymers Containing 3-Indolylfulgides/Indolylfulgimides

Fulgides and fulgimides are important organic photochromic compounds and can switch between the open forms and the closed forms with light. The 3-indolylfulgides and 3-indolylfulgimides exhibit promising photochromic properties and have great potential in optical memory devices, optical switches and biosensors. Copolymers containing 3-indolylfulgides/indolylfulgimides synthesized via free radical polymerizations increase conformation changes and allow the photochromic compounds to be uniformly distributed in the polymer matrix. A trifluoromethyl 3-indolylfulgide and two trifluoromethyl 3-indolylfulgimides with one or two polymerizable N-stryryl group(s) were prepared. Copolymerization with methyl methacrylate provided two linear copolymers or a cross-linked copolymer. The properties of the monomeric fulgide/fulgimides and copolymers in toluene or as thin films were characterized. In general, the photochromic monomers and copolymers revealed similar photochromic properties and exhibited good thermal and photochemical stability. All compounds absorb visible light in both open forms and closed forms. The closed form copolymers were more stable than the open form copolymers and showed little or no degradation after 400 h. The photochemical degradation rate was less than 0.03% per cycle. In films, conformational restrictions were observed for the open forms suggesting that the preparation of films from the closed forms is advantageous. Two novel methyl 3-indolylfulgimides with one or two polymerizable N-stryryl group(s) were prepared. Copolymerization of acrylamide with the methyl indolylfulgimides or the trifluoromethyl indolylfulgimides yielded two aqueous soluble linear copolymers and two photochromic hydrogels. The closed form copolymers containing trifluoromethyl indolylfulgimides were hydrolyzed in aqueous solution by replacing the trifluoromethyl group with a carboxylic acid group. The resulting carboxylic copolymers were also photochromic. The copolymers containing methyl fulgimides were stable in aqueous solutions and did not hydrolyze. Both methyl and carboxylic copolymers exhibited good stability in aqueous solutions. In general, the open form copolymers were more stable than the closed form copolymers, and the copolymers revealed better stability in acidic solution than neutral solution. The linear copolymers displayed better photochemical stability in neutral solution and degraded up to 22% after 105 cycles. In contrast, the hydrogels showed enhanced fatigue resistance in acidic condition and underwent up to 60 cycles before degrading 24%.

Changes in temporomandibular joint disc position and form following Herbst and fixed orthodontic treatment

Objective: To determine the changes in the position and form of the temporomandibular joint articular disc in adolescents with Class II division 1 malocclusion and mandibular retrognathism treated with the Herbst appliance (phase I) and fixed orthodontic appliance (phase II). Materials and Methods: Thirty-two consecutive adolescents went through phase I of treatment and 23 completed phase II. The temporomandibular joints were evaluated qualitatively by means of magnetic resonance images at the beginning of treatment (T1), during phase I (T2), at the end of phase I (T3), and at the end of phase II (T4). Results: Significant changes in disc position were not observed with the mouth closed between T1 X T3 (P = .317), T3 X T4 (P = .287), or T1 X T4 (P = .261). At T2, on average, the disc was positioned regressively. With the mouth open, no difference was observed between T1 X T3 (P = .223) or T1 X T4 (P = .082). We did observe a significant difference between T3 X T4 (P < .05). Significant changes in the disc form were found with the mouth closed between T1 X T2 (P < .001) and T2 X T3 (P < .001). Conclusions: At the end of the two-phase treatment, in general terms, the position and form of the initial articular discs were maintained; however, in some temporomandibular joints some seemingly adverse effects were observed at T4. (Angle Orthod. 2010;80:843-852.)

Interaction of RTD-1, a cyclic antimicrobial defensin from Rhesus macaque leukocytes, and its open chain analogue with membrane mimics

In contrast to other mammalian defensins, rhesus theta defensin-1 (RTD-1) is composed of just 18 amino acids with the backbone cyclized through peptide bonds. Antibacterial activities of both the native cyclic peptide and a linear form were examined, showing that the cyclic form was 3-fold more active than the open chain analogue, oRTD-1, although both peptides adopt very similar structures in water. It was suggested that the additional charges at the termini of oRTD-1 are the cause for its lower antimicrobial activity. Therefore, we studied the interaction of both peptides with membrane mimics composed of zwitterionic (PC) and negatively charged (PG) phospholipids, major lipid components of erythrocyte and bacterial cell membranes, respectively. Microcalorimetry showed that RTD-1 and oRTD-1 did not affect the phase behavior of PC liposomes, while in PG liposomes both peptides induced new phase transitions above the chain melting transition of the lipid. The shape and fraction differed between both peptides, depending also on their concentration, which will be discussed in terms of their antimicrobial activity.

Hippocampus lipid peroxidation induced by residual oil fly ash intranasal instillation versus habituation to the open field

Epidemiological studies have demonstrated the adverse effects of particulate matter (PM) inhalation on the respiratory and cardiovascular systems. It has been reported that air pollution may affect the central nervous system and decrease cognitive function. In rats, residual oil fly ash (ROFA) instillation causes decreased motor activity and increased lipid peroxidation in the striatum and the cerebellum. Our objective was to determine whether chronic instillation of particles induces changes in learning and memory in rats and whether oxidants in the hippocampus may contribute to these adverse effects. Forty-five-day-old male Wistar rats were exposed to ROFA by intranasal instillation and were treated with N-acetylcysteine (NAC) at 150 mg/kg i.p. for 30 days. Control groups were exposed to ROFA, NAC, or neither. On days 1, 8, and 30 of the protocol, rats were submitted to the open field test to evaluate habituation. After the last open field session, the rats were killed by decapitation. The hippocampus was used to determine lipid peroxidation (LP) by the thiobarbituric acid-reactive substances test. ROFA instillation induced an increase in LP in the hippocampus compared to all treatment groups (p = .012). NAC treatment blocked these changes. All of the treatment groups presented a decrease in the frequency of peripheral walking (p = .001), rearing (p = .001), and exploration (p = .001) over time. Our study demonstrates that exposure to particles for 30 days and/or NAC treatment do not modify habituation to an open field, a simple form of learning and memory in rats, and that oxidative damage induced by ROFA does not modulate these processes.