Diversidade de geofungos em águas do Parque Municipal do Ibirapuera na cidade de São Paulo, SP, Brasil

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Avaliação do acesso à saúde aos níveis de atenção de maior complexidade no município de Marília/SP, sob a ótica da integralidade

Pós-graduação em Enfermagem (mestrado profissional) - FMB

Variação espaço-temporal do microfitoplâncton na região da foz do rio Guamá (estuário amazônico), Belém, PA

O sistema hidrográfico de Belém é constituído por dois grandes corpos hídricos: a baía do Guajará e o rio Guamá, cujo divisor de águas é quase imperceptível. A importância do rio Guamá para a cidade de Belém deve-se ao fato de que esse juntamente com os lagos Água Preta e Bolonha, faz parte do Complexo Hídrico do Utinga, manancial que abastece a cidade. O estudo visou caracterizar a variação espaço-temporal da comunidade microfitoplanctônica nessa região, durante um ciclo anual, em período de maior e menor precipitação pluviométrica, em cinco estações de coleta. As amostras qualitativas foram coletadas com rede de plâncton de 20 μm. Para o estudo quantitativo, foram coletadas diretamente na sub-superfície da água com frascos de polietileno de 250 ml. O material biológico foi fixado com solução Transeau. Simultaneamente, foram registrados os parâmetros abióticos na superfície da água. Os fatores hidrológicos não apresentaram variações relevantes entre as estações e os períodos sazonais. Foram identificadas 173 espécies, destacando-se as diatomáceas como grupo de maior densidade e que caracteriza o ambiente. Não foram observadas espécies dominantes durante o período estudado. Através da abundância relativa, constatou-se que a maioria dos organismos foi considerada rara. A diversidade específica variou de muito baixa a alta, sendo observados baixos índices de diversidade no período menos chuvoso, destacando-se a ocorrência das espécies Aulacoseira granulata (Ehrenb.) Ralfs, Actinoptychus sp. e Cyclotella sp. Já a densidade fitoplanctônica apresentou variação temporal definida, sendo registrados os maiores florescimentos durante o período mais chuvoso. Quanto à variação espacial, não houve um padrão em relação aos períodos sazonais. As euglenofíceas foram pouco freqüentes ou esporádicas e se restringiram ao período menos chuvoso, já os dinoflagelados estiveram presentes nos dois períodos, embora considerados organismos marinhos, foram registradas duas espécies do gênero Peridinium. A comunidade fitoplanctônica não apresentou diferenças significativas entre as estações de coleta, provavelmente devido à hidrodinâmica e à forte drenagem fluvial do rio Guamá.

Um estudo da estabilidade mecânica de poços a partir de perfis geofísicos em formações pouco consolidadas

A análise da estabilidade mecânica de um poço pode ser feita a partir do cálculo de parâmetros elásticos da formação utilizando a densidade do meio e as velocidades de propagação das ondas compressional e cisalhante na formação rochosa, os quais podem ser obtidos de perfis geofísicos do poço. Em formações sedimentares pouco consolidadas as ferramentas de perfilagem sônica convencionais (monopolares) não conseguem registrar com acuidade a velocidade da onda cisalhante pois a primeira chegada dessa onda é camuflada pela chegada de outras ondas que podem ser mais rápidas que a onda cisalhante num poço perfurado neste tipo de formação. Medidas das velocidades sônicas são feitas em laboratório em amostras da formação, sob condições semelhantes às condições in situ, servindo como ajuste das velocidades registradas no poço pela ferramenta de perfilagem sônica. Para a análise de estabilidade da formação, perfis auxiliares são necessários como o perfil de porosidade, saturação de fluidos e perfis de composição mineralógica da formação rochosa. Exige-se ainda dados de testes de avaliação da formação e de condições do reservatório, mas que são comuns em poços de petróleo, como o teste de formação e os testes de pressurização do poço, tais como o teste de micro-fraturamento hidráulico ou o teste de absorção. A avaliação das tensões principais efetivas que atuam distante do poço, e que não são afetadas pela sua presença, é feita através da associação de um modelo de deformação elástica apropriado e o resultado do teste de pressurização disponível para o poço em estudo. Utilizando resultados clássicos da teoria da elasticidade geral pode-se calcular o campo de tensões modificado na vizinhança da parede do poço devido ao efeito da própria presença do poço ali perfurado e da diferença de pressão existente entre o interior do poço e a formação rochosa. A determinação das propriedades mecânicas da formação a partir das velocidades sônicas e a avaliação do campo de tensões assumindo um modelo elástico de deformação, supõem o meio rochoso no qual as ondas se propagam como elástico, homogêneo e isotrópico. Esta suposição representa a principal aproximação assumida pela metodologia descrita neste trabalho. De posse das propriedades mecânicas da formação e do campo de tensões que age na vizinhança do poço resta definir o critério segundo o qual a rocha sofre instabilidade mecânica quando submetida aquele campo de tensões. Isto permite determinar se, nas condições avaliadas do poço e da formação, haverá quebra da parede do poço por excesso de tensão e, se houver, qual a sua extensão. Assim o problema é como analisar o comportamento mecânico de um poço em uma formação pouco consolidada a partir de perfis geofísicos os quais podem ter problemas no registro das propriedades físicas do meio em formações deste tipo. A metodologia proposta é aplicada a dois intervalos de profundidade pertencentes a dois poços onde arenitos e folhelhos se intercalam e nos quais todos os dados necessários estão disponíveis. Os resultados obtidos mostram que, exceto quando outros mecanismos de quebra da parede do poço agem na formação, a metodologia proposta consegue com sucesso detectar zonas de ocorrência de instabilidade mecânica do poço provocadas por um campo de tensões que excede a resistência mecânica da formação.

Avaliação dos parâmetros abióticos e caracterização da comunidade planctônica em um viveiro de cultivo de Litopenaeus vannamei (Boone, 1931) no município de Curuçá - Pará

Este trabalho objetivou avaliar durante um ciclo de cultivo de Litopenaeus vannamei com periodicidade quinzenal de 20/09/08 a 05/12/08 a comunidade planctônica e os parâmetros abióticos em duas estações dentro de um viveiro no município de Curuça, Estado do Pará. Foram medidos transparência, pH, oxigênio dissolvido, salinidade e temperatura, sendo os quatro últimos registrados na superfície e próximo ao fundo e realizadas coletas para o estudo do microfitoplâncton, zooplâncton e clorofila “a”. A temperatura variou de 31,5ºC a 35ºC. O oxigênio dissolvido variou de 4,2 mg/l a 15,5 mg/l. O pH manteve-se ligeiramente alcalino, entre 8,1 e 9,4. A menor salinidade foi 26,9 e a maior, 30 ppm. A transparência diminuiu de 55 cm para 17 cm. Clorofila a teve um mínimo de 2,33mg/m³ e um máximo de 471,34 mg/m³. Foram identificados 95 taxa e Bacillariophyta foi o grupo mais importante, sendo Navicula, Pleurosigma e Nitzschia os principais responsáveis pela sua dominância. A maior densidade registrada para o microfitoplâncton foi de 104.400 org/l no início do cultivo (20/09) e a menor foi 3.600 org/l na última coleta (05/12). A média de diversidade para o fitoplâncton na Estação 01 foi 1,49 bits/ind e na Estação 02, 1,43 bits/ind. Foram identificados 34 taxa zooplanctônicos, sendo Copepoda o grupo mais importante e Acartia lilljeborgi, Euterpina acutifrons, Oithona hebes, Oithona oswaldocruzzi e Parvocalanus crassirostris os principais responsáveis pela sua dominância. A maior densidade registrada para o zooplâncton foi de 162.000 org/m³ no início do cultivo (20/09) e a menor foi 375 org/m³ no dia 05/11. A diversidade também foi baixa tendo médias de 1,34 bits/ind e 1,10 bits/ind nas estações 01 e 02, respectivamente. Entre as principais conclusões: a comunidade microfitoplanctônica foi dominada pelas diatomáceas, sendo os principais gêneros responsáveis por esta dominância: Pleurosigma, Nitzschia e Navicula e a divisão Bacillariophyta foi o grupo mais importante tanto em termos de riqueza quanto de densidade; a classe dinophyceae revelou estar melhor adaptados em águas mais claras; os copépodos foram dominantes, sendo Acartia lilljeborgi, Oithona hebes, Oithona oswaldocruzzi, Parvocalanus crassirostris e Euterpina acutifrons as espécies que mais contribuíram para esta dominância; Clorofila “a” respondeu aos maiores aportes de ração durante o cultivo, aumentando com o tempo; as variáveis físico-químicas que sofreram influência do cultivo, variando significativamente ao longo do tempo foram: pH, oxigênio dissolvido e transparência e o viveiro investigado foi considerado homogêneo avaliando sua profundidade e área.

Benthic foraminiferal distribution on the southeastern Brazilian shelf and upper slope

Foraminiferal data were obtained from 66 samples of box cores on the southeastern Brazilian upper margin (between 23.8A degrees-25.9A degrees S and 42.8A degrees-46.13A degrees W) to evaluate the benthic foraminiferal fauna distribution and its relation to some selected abiotic parameters. We focused on areas with different primary production regimes on the southern Brazilian margin, which is generally considered as an oligotrophic region. The total density (D), richness (R), mean diversity (H) over bar`, average living depth (ALD(X) ) and percentages of specimens of different microhabitats (epifauna, shallow infauna, intermediate infauna and deep infauna) were analyzed. The dominant species identified were Uvigerina spp., Globocassidulina subglobosa, Bulimina marginata, Adercotryma wrighti, Islandiella norcrossi, Rhizammina spp. and Brizalina sp.. We also established a set of mathematical functions for analyzing the vertical foraminiferal distribution patterns, providing a quantitative tool that allows correlating the microfaunal density distributions with abiotic factors. In general, the cores that fit with pure exponential decaying functions were related to the oligotrophic conditions prevalent on the Brazilian margin and to the flow of the Brazilian Current (BC). Different foraminiferal responses were identified in cores located in higher productivity zones, such as the northern and the southern region of the study area, where high percentages of infauna were encountered in these cores, and the functions used to fit these profiles differ appreciably from a pure exponential function, as a response of the significant living fauna in deeper layers of the sediment. One of the main factors supporting the different foraminiferal assemblage responses may be related to the differences in primary productivity of the water column and, consequently, in the estimated carbon flux to the sea floor. Nevertheless, also bottom water velocities, substrate type and water depth need to be considered.

Spatial and Temporal Variation of Archaeal, Bacterial and Fungal Communities in Agricultural Soils

Background: Soil microbial communities are in constant change at many different temporal and spatial scales. However, the importance of these changes to the turnover of the soil microbial communities has been rarely studied simultaneously in space and time. Methodology/Principal Findings: In this study, we explored the temporal and spatial responses of soil bacterial, archaeal and fungal beta-diversities to abiotic parameters. Taking into account data from a 3-year sampling period, we analyzed the abundances and community structures of Archaea, Bacteria and Fungi along with key soil chemical parameters. We questioned how these abiotic variables influence the turnover of bacterial, archaeal and fungal communities and how they impact the long-term patterns of changes of the aforementioned soil communities. Interestingly, we found that the bacterial and fungal b-diversities are quite stable over time, whereas archaeal diversity showed significantly higher fluctuations. These fluctuations were reflected in temporal turnover caused by soil management through addition of N-fertilizers. Conclusions: Our study showed that management practices applied to agricultural soils might not significantly affect the bacterial and fungal communities, but cause slow and long-term changes in the abundance and structure of the archaeal community. Moreover, the results suggest that, to different extents, abiotic and biotic factors determine the community assembly of archaeal, bacterial and fungal communities.

Effects of habitat characteristics on cryptic fish assemblages

Habitat structure is known to influence the abundance of fishes on temperate reefs. Biotic interactions play a major role in determining the distribution and abundance of species. The significance of these forces in affecting the abundance of fishes may hinge on the presence of organisms that either create or alter habitat. On temperate reefs, for example, macroalgae are considered autogenic ecosystem engineers because they control resource availability to other species through their physical structure and provide much of the structure used by fish. On both coral and temperate reefs, small cryptic reef fishes may comprise up to half of the fish numbers and constitute a diverse community containing many specialized species. Small cryptic fishes (<100 mm total length) may be responsible for the passage of 57% of the energy flow and constitute ca. 35% of the overall reef fish biomass on coral reefs. These benthic fish exploit restricted habitats where food and shelter are obtained in, or in relation to, conditions of substrate complexity and/or restricted living space. A range of mechanisms has been proposed to account for the diversity and the abundance of small fishes: (1) lifehistory strategies that promote short generation times, (2) habitat associations and behaviour that reduce predation and (3) resource partitioning that allows small species to coexist with larger competitors. Despite their abundance and potential importance within reef systems, little is known of the community ecology of cryptic fishes. Specifically on habitat associations many theories suggested a not clear direction on this subject. My research contributes to the development of marine fish ecology by addressing the effects of habitat characteristics upon distribution of cryptobenthic fish assemblages. My focus was on the important shallow, coastal ecosystems that often serve as nursery habitat for many fish and where different type of habitat is likely to both play important roles in organism distribution and survival. My research included three related studies: (1) identification of structuring forces on cryptic fish assemblages, such as physical and biological forcing; (2) macroalgae as potential tools for cryptic fish and identification of different habitat feature that could explain cryptic fish assemblages distribution; (3) canopy formers loss: consequences on cryptic fish and relationship with benthos modifications. I found that: (1) cryptic fish assemblages differ between landward and seaward sides of coastal breakwaters in Adriatic Sea. These differences are explained by 50% of the habitat characteristics on two sides, mainly due to presence of the Codium fragile, sand and oyster assemblages. Microhabitat structure influence cryptic fish assemblages. (2) Different habitat support different cryptic fish assemblages. High heterogeneity on benthic assemblages reflect different fish assemblages. Biogenic components that explain different and diverse cryptic fish assemblages are: anemonia bed, mussel bed, macroalgal stands and Cystoseira barbata, as canopy formers. (3) Canopy forming loss is not relevant in structuring directly cryptic fish assemblages. A removal of canopy forming algae did not affect the structure of cryptic fish assemblages. Canopy formers algae on Conero cliff, does not seem to act as structuring force, probably due to its regressive status. In conclusion, cryptic fish have been shown to have species-specific associations with habitat features relating to the biological and non biological components afforded by fish. Canopy formers algae do not explain cryptic fish assemblages distribution and the results of this study and information from the literature (both from the Mediterranean Sea and elsewhere) show that there are no univocal responses of fish assemblages. Further exanimations on an non regressive status of Cystoseira canopy habitat are needed to define and evaluate the relationship between canopy formers and fish on Mediterranean sea.

Supramolecular order and dynamics of functional materials studied by solid state NMR

The goal of this thesis was the investigation of the structure, conformation, supramolecular order and molecular dynamics of different classes of functional materials (phthalocyanine, perylene and hexa-peri-hexabenzocoronene derivatives and mixtures of those), all having planar aromatic cores modified with various types of alkyl chains. The planar aromatic systems are known to stack in the solid and the liquid-crystalline state due to p-p interactions forming columnar superstructures with high one-dimensional charge carrier mobility and potential application in photovoltaic devices. The different functionalities attached to the aromatic cores significantly influence the behavior of these systems allowing the experimentalists to modify the structures to fine-tune the desired thermotropic properties or charge carrier mobility. The aim of the presented studies was to understand the interplay between the driving forces causing self-assembly by relating the structural and dynamic information about the investigated systems. The supramolecular organization is investigated by applying 1H solid state NMR recoupling techniques. The results are related with DSC and X-ray scattering data. Detailed information about the site-specific molecular dynamics is gained by recording spinning sideband patterns using 1H-1H and 13C-1H solid state NMR recoupling techniques. The determined dipole-dipole coupling constants are then related with the coupling constants of the respective rigid pairs, thus providing local dynamic order parameters for the respective moieties. The investigations presented reveal that in the crystalline state the preferred arrangement in the columnar stack of discotic molecules modified with alkyl chains is tilted. This leads to characteristic differences in the 1H chemical shifts of otherwise chemically equivalent protons. Introducing branches and increasing the length of the alkyl chains results in lower mesophase transitions and disordered columnar stacks. In the liquid-crystalline state some of the discs lose the tilted orientation, others do not, but all start a rapid rotation about the columnar axis.

Development of a field method to assess root parasites of woody plants - ecological analyses of the grapevine-phylloxera interaction

The development and the growth of plants is strongly affected by the interactions between roots, rootrnassociated organisms and rhizosphere communities. Methods to assess such interactions are hardly torndevelop particularly in perennial and woody plants, due to their complex root system structure and theirrntemporal change in physiology patterns. In this respect, grape root systems are not investigated veryrnwell. The aim of the present work was the development of a method to assess and predict interactionsrnat the root system of rootstocks (Vitis berlandieri x Vitis riparia) in field. To achieve this aim, grapernphylloxera (Daktulosphaira vitifoliae Fitch, Hemiptera, Aphidoidea) was used as a graperoot parasitizingrnmodel.rnTo develop the methodical approach, a longt-term trial (2006-2009) was arranged on a commercial usedrnvineyard in Geisenheim/Rheingau. All 2 to 8 weeks the top most 20 cm of soil under the foliage wallrnwere investigated and root material was extracted (n=8-10). To include temporal, spatial and cultivarrnspecific root system dynamics, the extracted root material was analyzed digitally on the morphologicalrnproperties. The grape phylloxera population was quantified and characterized visually on base of theirrnlarvalstages (oviparous, non oviparous and winged preliminary stages). Infection patches (nodosities)rnwere characterized visually as well, partly supported by digital root color analyses. Due to the knownrneffects of fungal endophytes on the vitality of grape phylloxera infested grapevines, fungal endophytesrnwere isolated from nodosity and root tissue and characterized (morphotypes) afterwards. Further abioticrnand biotic soil conditions of the vineyards were assessed. The temporal, spatial and cultivar specificrnsensitivity of single parameters were analyzed by omnibus tests (ANOVAs) and adjacent post-hoc tests.rnThe relations between different parameters were analyzed by multiple regression models.rnQuantitative parameters to assess the degeneration of nodosity, the development nodosity attachedrnroots and to differentiate between nodosities and other root swellings in field were developed. Significantrndifferences were shown between root dynamic including parameters and root dynamic ignoringrnparameters. Regarding the description of grape phylloxera population and root system dynamic, thernmethod showed a high temporal, spatial and cultivar specific sensitivity. Further, specific differencesrncould be shown in the frequency of endophyte morphotypes between root and nodosity tissue as wellrnas between cultivars. Degeneration of nodosities as well as nodosity occupation rates could be relatedrnto the calculated abundances of grape phylloxera population. Further ecological questions consideringrngrape root development (e.g. relation between moisture and root development) and grape phylloxerarnpopulation development (e.g. relation between temperature and population structure) could be answeredrnfor field conditions.rnGenerally, the presented work provides an approach to evaluate vitality of grape root systems. Thisrnapproach can be useful, considering the development of control strategies against soilborne pests inrnviticulture (e.g. grape phylloxera, Sorospheara viticola, Roesleria subterranea (Weinm.) Redhaed) as well as considering the evaluation of integrated management systems in viticulture.

Effects of oligotrophication on primary production in peri-alpine lakes

During the second half of the 20th century untreated sewage released from housing and industry into natural waters led to a degradation of many freshwater lakes and reservoirs worldwide. In order to mitigate eutrophication, wastewater treatment plants, including Fe-induced phosphorus precipitation, were implemented throughout the industrialized world, leading to reoligotrophication in many freshwater lakes. To understand and assess the effects of reoligotrophication on primary productivity, we analyzed 28 years of 14C assimilation rates, as well as other biotic and abiotic parameters, such as global radiation, nutrient concentrations and plankton densities in peri-alpine Lake Lucerne, Switzerland. Using a simple productivity-light relationship, we estimated continuous primary production and discussed the relation between productivity and observed limnological parameters. Furthermore, we assessed the uncertainty of our modeling approach based on monthly 14C assimilation measurements using Monte Carlo simulations. Results confirm that monthly sampling of productivity is sufficient for identifying long-term trends in productivity and that conservation management has successfully improved water quality during the past three decades via reducing nutrients and primary production in the lake. However, even though nutrient concentrations have remained constant in recent years, annual primary production varies significantly from year to year. Despite the fact that nutrient concentrations have decreased by more than an order of magnitude, primary production has decreased only slightly. These results suggest that primary production correlates well to nutrients availability but meteorological conditions lead to interannual variability regardless of the trophic status of the lake. Accordingly, in oligotrophic freshwaters meteorological forcing may reduce productivity impacting on the entire food chain of the ecosystem.

EEG microstates during resting represent personality differences

We investigated the spontaneous brain electric activity of 13 skeptics and 16 believers in paranormal phenomena; they were university students assessed with a self-report scale about paranormal beliefs. 33-channel EEG recordings during no-task resting were processed as sequences of momentary potential distribution maps. Based on the maps at peak times of Global Field Power, the sequences were parsed into segments of quasi-stable potential distribution, the 'microstates'. The microstates were clustered into four classes of map topographies (A-D). Analysis of the microstate parameters time coverage, occurrence frequency and duration as well as the temporal sequence (syntax) of the microstate classes revealed significant differences: Believers had a higher coverage and occurrence of class B, tended to decreased coverage and occurrence of class C, and showed a predominant sequence of microstate concatenations from A to C to B to A that was reversed in skeptics (A to B to C to A). Microstates of different topographies, putative "atoms of thought", are hypothesized to represent different types of information processing.The study demonstrates that personality differences can be detected in resting EEG microstate parameters and microstate syntax. Microstate analysis yielded no conclusive evidence for the hypothesized relation between paranormal belief and schizophrenia.

Response to neoadjuvant treatment of invasive ductal breast carcinomas including outcome evaluation: MRI analysis by an automatic CAD system in comparison to visual evaluation

BACKGROUND The aim of this study was to evaluate imaging-based response to standardized neoadjuvant chemotherapy (NACT) regimen by dynamic contrast-enhanced magnetic resonance mammography (DCE-MRM), whereas MR images were analyzed by an automatic computer-assisted diagnosis (CAD) system in comparison to visual evaluation. MRI findings were correlated with histopathologic response to NACT and also with the occurrence of metastases in a follow-up analysis. PATIENTS AND METHODS Fifty-four patients with invasive ductal breast carcinomas received two identical MRI examinations (before and after NACT; 1.5T, contrast medium gadoteric acid). Pre-therapeutic images were compared with post-therapeutic examinations by CAD and two blinded human observers, considering morphologic and dynamic MRI parameters as well as tumor size measurements. Imaging-assessed response to NACT was compared with histopathologically verified response. All clinical, histopathologic, and DCE-MRM parameters were correlated with the occurrence of distant metastases. RESULTS Initial and post-initial dynamic parameters significantly changed between pre- and post-therapeutic DCE-MRM. Visually evaluated DCE-MRM revealed sensitivity of 85.7%, specificity of 91.7%, and diagnostic accuracy of 87.0% in evaluating the response to NACT compared to histopathology. CAD analysis led to more false-negative findings (37.0%) compared to visual evaluation (11.1%), resulting in sensitivity of 52.4%, specificity of 100.0%, and diagnostic accuracy of 63.0%. The following dynamic MRI parameters showed significant associations to occurring metastases: Post-initial curve type before NACT (entire lesions, calculated by CAD) and post-initial curve type of the most enhancing tumor parts after NACT (calculated by CAD and manually). CONCLUSIONS In the accurate evaluation of response to neoadjuvant treatment, CAD systems can provide useful additional information due to the high specificity; however, they cannot replace visual imaging evaluation. Besides traditional prognostic factors, contrast medium-induced dynamic MRI parameters reveal significant associations to patient outcome, i.e. occurrence of distant metastases.

Soft-bottom macrobenthic faunal associations in the southern Chilean glacial fjord complex

Macrobenthic associations were investigated at 29 sampling stations with a semi-quantitative Agassiz trawl, ranging from the South Patagonian Icefield to the Straits of Magellan in the South Chilean fjord system. A total of 1,895 individuals belonging to 131 species were collected. 19 species belong to colonial organisms, mainly Bryozoa (17 species) and Octocorallia (2 species). The phylum Echinodermata was the most diverse in species number (47 species), with asteroids (25 species) and ophiuroids (13 species) being the best represented within this taxon. Polychaeta was the second dominant group in terms of species richness (46 species). Multidimensional scaling ordination (MDS) separated two station groups, one related to fjords and channels off the South Patagonian Icefield and the second one to stations surrounding the Straits of Magellan. 45 species account for 90% of the dissimilarity between these two groups. These differences can mainly be explained by the influence of local environmental conditions determined by processes closely related to the pres- ence/absence of glaciers. Abiotic parameters such as water depth, type of sediment and chemical features of the superficial sediment were not correlated with the numbers of individuals caught by the Agassiz trawl in each group of sampling stations.

A coupled proton-transfer and twisting-motion fluorescence probe for lipid bilayers

A new and sensitive molecular probe, 2-(2′-hydroxyphenyl)imidazo[1,2-a]pyridine (HPIP), for monitoring structural changes in lipid bilayers is presented. Migration of HPIP from water into vesicles involves rupture of hydrogen (H) bonds with water and formation of an internal H bond once the probe is inside the vesicle. These structural changes of the dye allow the occurrence of a photoinduced intramolecular proton-transfer reaction and a subsequent twisting/rotational process upon electronic excitation of the probe. The resulting large Stokes-shifted fluorescence band depends on the twisting motion of the zwitterionic phototautomer and is characterized in vesicles of dimyristoyl-phosphatidylcholine and in dipalmitoyl-phosphatidylcholine at the temperature range of interest and in the presence of cholesterol. Because the fluorescence of aqueous HPIP does not interfere in the emission of the probe within the vesicles, HPIP proton-transfer/twisting motion fluorescence directly allows us to monitor and quantify structural changes within bilayers. The static and dynamic fluorescence parameters are sensitive enough to such changes to suggest this photostable dye as a potential molecular probe of the physical properties of lipid bilayers.