Interaction of cationic water-soluble meso-tetrakis(4-N-methylpyridiniumyl)porphyrin (TMPyP) with ionic and nonionic micelles: aggregation and binding

The equilibrium of meso-tetrakis(4-N-methylpyridiniumyl)porphyrin (TMPyP) in aqueous solution in the presence of surfactants was studied by optical spectroscopic techniques and SAXS (small angle X-ray scattering). Anionic SDS (sodium dodecyl sulfate), zwitterionic HPS (N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate) and nonionic TRITON X-100 (t-octyl-phenoxypolyethoxyethanol), surfactants were used. TMPyP is characterized by a protonation equilibrium with a pK(a) around 1.0, associated with the diacid-free base transition, and a second pK(a) around 12.0 related with the transition between the free base and the monoanion form. Three independent species were observed for TMPyP at pH 6.0 as a function of SDS concentration: free TMPyP, TMPyP-SDS aggregates and porphyrin monomer bound to micelles. For HPS and TRITON X-100, the equilibrium of TMPyP as a function of pH is quite similar to that obtained in pure aqueous solution: no aggregation was observed, suggesting that electrostatic contribution is the major factor in the interaction between TMPyP and surfactants. SAXS data analysis demonstrated a prolate ellipsoidal shape for SDS micelles; no significant changes in shape and size were observed for SDS-TMPyP co-micelles. Moreover, the ionization coefficient, alpha, decreases with the increase of the porphyrin concentration, suggesting the ""screening"" of the anionic charge of SDS by the cationic porphyrin. These results are consistent with optical absorption, fluorescence and RLS (resonance light scattering) spectroscopies data, allowing to conclude that neutral surfactants present a smaller interaction with the cationic porphyrin as compared with an ionic surfactant. Therefore, the interaction of TMPyP with the ionic and nonionic surfactants is predominantly due to the electrostatic contribution. Copyright (c) 2008 Society of Porphyrins & Phthalocyanines.

Excited-state dynamics of meso-tetrakis(sulfonatophenyl) porphyrin J-aggregates

The excited-state dynamics of free-base meso-tetrakis(sulfonatophenyl) porphyrin J-aggregates obtained by the Z-scan technique in femto- and picosecond time scales, along with UV-Vis spectroscopy and flash photolysis is reported. Besides obtaining the S-1 state lifetime, the discrimination between internal conversion and intersystem crossing nonradiative processes from that state was also possible, and their rates and respective quantum yields were found. The aggregates present reverse saturable absorption at 532 nm for both singlet and triplet excited states. The data shown is important for several applications such as optical limiting, photodynamic therapy and others. (C) 2011 Elsevier B.V. All rights reserved.

Interaction of the meso-tetrakis (4-N-methylpyridyl) porphyrin with gel and liquid state phospholipid vesicles

The interaction of the cationic meso-tetrakis 4-N-methylpyridyl porphyrin (TMPyP) with large unilamellar vesicles (LUVs) was investigated in the present study. LUVs were formed by mixtures of the zwitterionic 1,2-dipalmitoyl-sn-glycero-phosphatidylcholine (DPPC) and anionic 1,2-dipalmitoyl-sn-glycero-3-phosphoglycerol (DPPG) phospholipids, at different DPPG molar percentages. All investigations were carried out above (50 degrees C) and below (25 degrees C) the main phase transition temperature of the LUVs (similar to 41 degrees C). The binding constant values, K-b, estimated from the time-resolved fluorescence study, showed a significant increase of the porphyrin affinity at higher mol% DPPG. This affinity is markedly increased when the LUVs are in the liquid crystalline state. For both situations, the increase of the K-b value was also followed by a higher porphyrin fraction bound to the LUVs. The displacement of the vesicle-bound porphyrins toward the aqueous medium, upon titration with the salt potassium chloride (KCl), was also studied. Altogether, our steady-state and frequency-domain fluorescence quenching data results indicate that the TMPyP is preferentially located at the LUVs Stern layer. This is supported by the zeta potential studies, where a partial neutralization of the LUVs surface charge, upon porphyrin titration, was observed. Dynamic light scattering (DLS) results showed that, for some phospholipid systems, this partial neutralization leads to the LUVs flocculation. (C) 2012 Elsevier Inc. All rights reserved.

Photodynamic Efficiency of Cationic meso-Porphyrins at Lipid Bilayers: Insights from Molecular Dynamics Simulations

Porphyrin derivatives have applications as photoactive drugs in photodynamic therapy. However, little is known about their interactions with phospholipid membranes at the molecular level. We employed molecular dynamics simulations to model the binding between a series of cationic meso-(N-methyl-4-pyridinium)phenylporphyrins and anionic phosphatidylglycerol lipid bilayers. This was done in the presence of molecular oxygen within the membrane. The ability of various porphyrins to cause photodamage was quantified in terms of their immersion depth and degree of exposition to a higher oxygen concentration inside the membrane. Simulations showed that the photodynamic efficiency could be improved as the number of hydrophobic phenyl substituents attached to the porphyrinic ring increased. In the specific case of porphyrins containing two hydrophobic and two charged substituents, the cis isomer was significantly more efficient than the trans. These results correlate well with previous experimental observations. They highlight the importance of both the total charge and amphiphilicity of the photosensitizer for its performance in photodynamic therapy.

Vertical distribution of benthic invertebrate larvae during an upwelling event along a transect off the tropical Brazilian continental margin

Abundance and composition of marine benthic communities have been relatively well studied in the SE Brazilian coast, but little is known on patterns controlling the distribution of their planktonic larval stages. A survey of larval abundance in the continental margin, using a Multi-Plankton Sampler, was conducted in a cross-shelf transect off Cabo Frio (23 degrees S and 42 degrees W) during a costal upwelling event. Hydrographic conditions were monitored through discrete CDT casts. Chlorophyll-a in the top 100 m of the water column was determined and changes in surface chlorophyll-a was estimated using SeaWiFS images. Based on the larval abundances and the meso-scale hydrodynamics scenario, our results suggest two different processes affecting larval distributions. High larval densities were found nearshore due to the upwelling event associated with high chlorophyll a and strong along shore current. On the continental slope, high larval abundance was associated with a clockwise rotating meander, which may have entrapped larvae from a region located further north (Cabo de Sao Tome, 22 degrees S and 41 degrees W). In mid-shelf areas, our data suggests that vertical migration may likely occur as a response to avoid offshore transport by upwelling plumes and/or cyclonic meanders. The hydrodynamic scenario observed in the study area has two distinct yet extremely important consequences: larval retention on food-rich upwelling areas and the broadening of the tropical domain to southernmost subtropical areas. (C) 2009 Elsevier B.V. All rights reserved.

Height variability from the MIROC - IPCC model for the 20th century compared to that of the TOPEX/POSEIDON altimeter

Planetary waves are key to large-scale dynamical adjustment in the global ocean as they transfer energy from the east to the west side of oceanic basins; they connect the forcing in the ocean interior with the variability at its boundaries: and they change the local heat content, thus coupling oceanic, atmospheric, and biological processes. Planetary waves, mostly of the first baroclinic mode, are observed as distinctive patterns in global time series of sea surface height anomaly (SSHA) and heat storage. The goal of this study is to compare and validate large-scale SSHA signals from coupled ocean-atmosphere general circulation Model for Interdisciplinary Research on Climate (MIROC) with TOPEX/POSEIDON satellite altimeter observations. The last decade of the models` time series is selected for comparison with the altimeter data. The wave patterns are separated from the meso- and large-scale SSHA signals by digital filters calibrated to select the same spectral bands in both model and altimeter data. The band-wise comparison allows for an assessment of the model skill to simulate the dynamical components of the observed wave field. Comparisons regarding both the seasonal cycle and the Rossby wave Held differ significantly among basins. When carried within the same basin, differences can occur between equal latitudes in opposite hemispheres. Furthermore, at some latitudes the MIROC reproduces biannual, annual and semiannual planetary waves with phase speeds and average amplitudes similar to those observed by the altimeter, but with significant differences in phase. (C) 2008 Elsevier Ltd. All rights reserved.

Coastal and shelf circulation in the vicinity of Camamu Bay (14 degrees S), Eastern Brazilian Shelf

The Camamu Bay (CMB) is located on the narrowest shelf along the South American coastline and close to the formation of two major Western Boundary Currents (WBC), the Brazil/North Brazil Current (BC/NBC). These WBC flow close to the shelf break/slope region and are expected to interact with the shelf currents due to the narrowness of the shelf. The shelf circulation is investigated in terms of current variability based on an original data set covering the 2002-2003 austral summer and the 2003 austral autumn. The Results show that the currents at the shelf are mainly wind driven, experiencing a complete reversal between seasons due to a similar change in the wind field. Currents at the inner-shelf have a polarized nature, with the alongshore velocity mostly driven by forcings at the sub-inertial frequency band and the cross-shore velocity mainly supra-inertially forced, with the tidal currents playing an important role at this direction. The contribution of the forcing mechanisms at the mid-shelf changes between seasons. During the summer, forcings in the two frequency bands are important to drive the currents with a similar contribution of the tidal currents. On the other hand, during the autumn season, the alongshore velocity is mostly driven by sub-inertial forcings and tidally driven currents still remain important in both directions. Moreover, during the autumn when the stratification is weaker, the response of the shelf currents to the wind forcing presents a barotropic signature. The meso-scale processes related to the WBC flowing at the shelf/slope region also affect the circulation within the shelf, which contribute to cause significant current reversals during the autumn season. Currents at the shelf-estuary connection are clearly supra-inertially forced with the tidal currents playing a key role in the generation of the along-channel velocities. The sub-inertial forcings at this location act mainly to drive the weak ebb currents which were highly correlated with both local and remote wind forcing during the summer season. (C) 2010 Elsevier Ltd. All rights reserved.

Correlation of photodynamic activity and singlet oxygen quantum yields in two series of hydrophobic monocationic porphyrins

The photodynamic properties of eight hydrophobic monocationic methyl and ruthenium polypyridine complex derivatives of free-base and zinc(II) meso-triphenyl-monopyridylporphyrin series were evaluated and compared using HeLa cells as model. The cream-like polymeric nanocapsule formulations of marine atelocollagen/xanthan gum, prepared by the coacervation method, exhibited high phototoxicity but negligible cytotoxicity in the dark. Interestingly, the formulations of a given series presented similar photodynamic activities but the methylated free-base derivatives were significantly more phototoxic than the respective ruthenated photosensitizers, reflecting the higher photoinduced singlet oxygen quantum yields of those monocationic porphyrin dyes.

Magmatism and fenitization in the Cretaceous potassium-alkaline-carbonatitic complex of Ipanema So Paulo State, Brazil

The Ipanema alkaline-carbonatitic complex is part of the Meso-Cenozoic alkaline magmatism located within the southeastern part of the Brazilian Platform. Drill-core and field sampling have indicated the occurrence of glimmerites, with subordinate shonkinites (mela-syenites), clinopyroxene-bearing glimmerites, diorites and syenites. The glimmerites are cross-cut by lamprophyric dykes and calciocarbonatites. Fenitization has deeply affected the country rocks, originating dioritic and syenitic rocks. The Ipanema rocks show a distinct potassic affinity. The initial Sr-Nd- isotopic composition of the Ipanema rocks ((87)Sr/(86)Sr = 0.70661-0.70754 and (143)Nd/(144)Nd = 0.51169-0.51181) is similar to that of tholeiitic and potassium-rich-alkaline rocks of the Eastern Paraguay. Stable isotope data for the Ipanema calciocarbonatite suggest interaction with fluids at temperatures typical of hydrothermal stages, as hypothesized for other carbonatite complexes from southeastern Brazil. The chemical differences between the lamprophyre, glimmerites, carbonatites, apatitites and magnetitites, and the absence of marked REE enrichment in the evolved lithologies, all indicate that fractional crystallization and accumulus of liquidus phases in a magma reservoir, likely coupled with liquid immiscibility processes, may have played an important role in the genesis of the Ipanema rocks.

Mechanism and Efficiency of Cell Death of Type II Photosensitizers: Effect of Zinc Chelation

A series of meso-substituted tetra-cationic porphyrins, which have methyl and octyl substituents, was studied in order to understand the effect of zinc chelation and photosensitizer subcellular localization in the mechanism of cell death. Zinc chelation does not change the photophysical properties of the photosensitizers (all molecules studied are type II photosensitizers) but affects considerably the interaction of the porphyrins with membranes, reducing mitochondrial accumulation. The total amount of intracellular reactive species induced by treating cells with photosensitizer and light is similar for zinc-chelated and free-base porphyrins that have the same alkyl substituent. Zinc-chelated porphyrins, which are poorly accumulated in mitochondria, show higher efficiency of cell death with features of apoptosis (higher MTT response compared with trypan blue staining, specific acridine orange/ethidium bromide staining, loss of mitochondrial transmembrane potential, stronger cytochrome c release and larger sub-G1 cell population), whereas nonchelated porphyrins, which are considerably more concentrated in mitochondria, triggered mainly necrotic cell death. We hypothesized that zinc-chelation protects the photoinduced properties of the porphyrins in the mitochondrial environment.

The influence of large-scale circulation, transient and local processes on the seasonal circulation of the Eastern Brazilian Shelf, 13 degrees S

The circulation at the Eastern Brazilian Shelf (EBS), near 13 degrees S, is discussed in terms of the currents and hydrography, associating large-scale circulation, transient and local processes to establish a regional picture of the EBS circulation. The results show that the circulation within the continental shelf and slope region is strongly affected by the seasonal changes in the wind field and mesa/large-scale circulation. Transient processes associated to the passage of Cold Front systems or meso-scale activity and the presence of a local canyon add more complexity to the system. During the austral spring and summer seasons, the prevailing upwelling favorable winds blowing from E-NE were responsible for driving southwestward shelf currents. The interaction with the Western Boundary Current (the Brazil Current), especially during summer, was significant and a considerable vertical shear in the velocity field was observed at the outer shelf. The passage of a Cold Front system during the springtime caused a complete reversal of the mean flow and contributed to the deepening of the Mixed Layer Depth (MLD). In addition, the presence of Salvador Canyon, subject to an upwelling favorable boundary current, enhanced the upwelling system, when compared to the upwelling observed at the adjacent shelf. During the austral autumn and winter seasons the prevailing downwelling favorable winds blowing from the SE acted to total reverse the shelf circulation, resulting in a northeastward flow. The passage of a strong Cold Front, during the autumn season, contributed not only to the strengthening of the flow but also to the deepening of the MLD. The presence of the Salvador Canyon, when subject to a downwelling favorable boundary current, caused an intensification of the downwelling process. Interestingly, the alongshore velocity at the shelf region adjacent to the head of the canyon was less affected when compared to the upwelling situation.

5-(1-(4-phenyl)-3-(4-nitrophenyl)triazene)-10,15,20-triphenylporphyrin: a new triazene-porphyrin dye and its spectroelectrochemical properties

The new triazene-porphyrin dye 5-(1-(4-phenyl)-3-(4-nitrophenyl)triazene)-10,15,20-triphenylporphyrin, encompassing a reactive protonated triazene moiety, was prepared starting from meso-tetraphenylporphyrin (H2TPP), first converting it to the 5-(4-nitrophenyl)-10,15,20-triphenylporphyrin, then reducing to the 5-(4-aminophenyl)-10,15,20-tri(phenyl) porphyrin intermediate, and reacting with the diazonium salt of 4-nitroaniline; and characterized by spectroscopic and electrochemical methods. The absorption spectrum of the neutral species resembled the sum of H2TPP and of 1,3-bis(4-nitrophenyl) triazene spectrum, but the deprotonated anionic species showed more delocalized frontier orbitals, behaving as a push-pull system exhibiting triazenide-to-porphyrin charge-transfer transitions.

Morfologia do funículo espermático em caprinos da raça Bhuj Brasileira

Estudamos em 40 caprinos adultos da raça Bhuj Brasileira os aspectos histológicos do funículo espermático. Observamos que este se acha envolvido por uma cápsula de tecido conjuntivo fibroelástico denso, de espessura variável, pregueada em alguns pontos, e revestida por mesotélio que circunda todo o conjunto vásculo-nervoso, e projeta-se para formar o mesoducto deferente. Em posição subcapsular, verifica- se uma camada de tecido conjuntivo fibroelástico frouxo, de espessura variável, que circunda parcialmente o funículo espermático, isolando nas regiões deferencial e abdeferencial, conjuntos vásculo-nervosos, responsáveis pela nutrição do epidídimo. Na região do mesoducto deferente, o tecido subcapsular acompanhado de tecido adiposo constitui a camada interna deste meso, formando a sua adventícia e abrigando vasos e nervos deferenciais. Na região abdeferencial, pequenos acúmulos de tecido adiposo são vistos de permeio aos vasos e nervos desta região. Entre as artérias, veias e nervos testiculares, bem como entre os vasos das regiões deferencial e abdeferencial, observa-se o tecido conjuntivo denso, intervascular, rico em fibras elásticas, que constitui as adventícias contínuas destes vasos. O arranjo vascular mostra que o segmento da artéria testicular, contido no funículo espermático, apresenta trajeto sinuoso. Estando envolvido pelo plexo venoso pampiniforme, formado por veias testiculares desprovidas de válvulas de calibres variados, apresentando amplas comunicações entre si. As veias responsáveis pela drenagem do epidídimo e ducto deferente estão localizadas em posição subcapsular deferencial e abdeferencial e mostram-se providas de válvulas. O trato das artérias testiculares no funículo espermático apresenta como média e desvio padrão 134,6±38,1cm à direita, e 137,0±33,9cm à esquerda, não existindo diferenças estatisticamente significantes ao nível de 5%, quando comparamos a média do segmento da artéria testicular contida no funículo espermático direito em relação ao esquerdo.

Variação do espectro das ondas de Rossby na região da frente Brasil-Malvinas

A média global da variação na quantidade de calor armazenado nos oceanos observada recentemente é positiva (Cabanes et al., 2001; Cazenave & Nerem, 2004), porém, sua distribuição espacial não é homogênea (Polito & Sato, 2008). O calor armazenado está associado, via expansão térmica, à altura da coluna d'água. Portanto, variações espaciais na tendência do calor armazenado tem como consequência mudanças na inclinação da superfície que, por sua vez, implicam em variações nas correntes geostróficas e portanto na energia cinética associada a fenômenos de meso e larga escala. Polito & Sato (2008) observaram tendências predominantemente positivas na amplitude de ondas de Rossby e vórtices de mesoescala nos últimos 13 anos, sugerindo que estes eventos estão, em uma média global, ficando mais energéticos. Estas tendências variam regionalmente e a variabilidade espacial é mais pronunciada próximo da extensão para leste das correntes de contorno oeste (CCO), sugerindo um aumento do cisalhamento da velocidade geostrófica. O afastamento das CCO da costa provoca, na região de sua ocorrência, intensa atividade vortical e meandramento, constituindo, do ponto de vista da anomalia da altura da superfície do mar (AASM), as áreas mais energéticas do planeta. O exemplo no Atlântico Sul é a separação da Corrente do Brasil (CB) em sua região de encontro com a Corrente das Malvinas (CM). A CB flui quase-meridionalmente para sul até aproximadamente 36°S, iniciando seu afastamento da costa até 38°S devido ao encontro de suas águas quentes e salinas com as águas de origem subpolar da CM, conforme Garzoli & Garrafo (1989). Essa região recebe o nome de Confluência Brasil-Malvinas (CBM).

Synthesis of self-assembled tubes in direct conjugated porphyrin-gold nanohybrid solution

We report on the formation of self-assembled meso-tetrakis (p-sulfonatofenyl) porphyrin (H2 TPP'S POT. 4-''IND. 4') tubes stabilized by gold nanoparticles (NPs) in basic solution and on their spectroscopic chareterization. The role of the gold NPs in the aggregation dynamics of free-base sulfonated porphyrin (H2TPP'S POT. 4-''IND. 4') is also investigated. The direct conjugation of the gold NPs to the H2TPPS4 molecule quenches the fluorescence intensity, while absorption peaks are blue-shifted, indicating predominant H-type aggregation. It is observed that porphyrin molecules adsorbed on the surface of the gold NP interact and form tubes of maximum diameter ∼1.5 μm and length >100 μm. Steady-state and time-resolved spectroscopic techniques confirm nonradiative energy transfer from porphyrin to gold NP.