Novel optical imaging technique to determine the 3-D orientation of collagen fibers in cartilage: variable-incidence angle polarization-sensitive optical coherence tomography

Objective: To investigate a novel optical method to determine the three dimensional (3-D) structure of articular cartilage collagen non-destructively. Methods: Polarization-sensitive optical coherence tomography was used to determine the apparent optical birefringence of articular cartilage for a number of different illumination directions. A quantitative method based on the theory of light propagation in uniaxial crystalline materials was validated on equine flexor tendon. Qualitative maps of fiber polar and azimuthal orientation at sites on the posterior and anterior segments of the equine third metacarpophalangeal (fetlock) joint were produced, and the azimuthal orientations compared with data from a split-line experiment. Results: Polar and azimuthal angles of cut flexor tendon broadly agreed with the nominal values but suggested that the accuracy was limited by our method of determining the apparent birefringence. On intact equine fetlock joints we found a non-zero polar tilt that changed in direction at various points along the apex, moving from the sagittal ridge outwards. The azimuthal orientation changes from being parallel to the sagittal ridge in the posterior region to being inclined to the ridge in the anterior region. This broadly agrees with split-line data for the anterior region but differs in the posterior region, possibly reflecting depth-dependent orientation changes. Conclusion: General quantitative agreement was found between our method and histology in validation experiments. Qualitative results for cartilage suggest a complicated 3-D structure that warrants further study. There is potential to develop this approach into a tool that can provide depth-resolved information on collagen orientation in near real-time, non-destructively and in vivo. (c) 2008 Osteoarthritis Research Society International. Published by Elsevier Ltd. All rights reserved

Spatial organisation and feeding ecology of the American mink (Mustela vison) in a coastal habitat

The American mink (Mustela vison Schreber) is the only introduced carnivore that has successfully colonised the British Isles. In the present study, the important problem of understanding which are the factors that limit or enhance their number has been addressed. A mink population (Mustela vison) inhabiting a coastal area of SW Scotland, was studied. The main purpose was to relate the spatial organisation of mink with spatial and temporal variations in the abundance and distribution of its prey, through the study of foraging strategies and habitat selection. Different scales of spatial organisation were considered. Foraging strategies (activity levels, habitat use, foraging behaviour) were found to vary over time and in areas with different habitat characteristics. The distribution and abundance of terrestrial prey was found to be important in determining such strategies, ultimately influencing mink densities. This observation supports the hypothesis of Clode and Macdonald (1995) on the influence of terrestrial prey on mink ability to disperse. Habitat selection of mink in the intertidal zone was studied here for the first time. Resident animals, which were foraging at low or mid tide, and within core areas were found to behave selectively, preferring areas with high prey abundance. In the intertidal zone, prey was most abundant in the lower shore, in areas without fresh water, and in areas with abundant and large rockpools. Mink showed preference for all these habitat characteristics. The nature of the substratum was also important in determining the abundance of prey out of rockpools. The results of this study are discussed in relation to limiting resources and competition with native carnivores. Finally a new home range estimator - the Density Circles method - was developed. This estimator is particularly suitable for describing home ranges presenting anomalous shapes, such as those found in mink

Decreased small mammals species diversity and increased population abundance along a gradient of agricultural intensification

Agricultural intensification has been widespread worldwide over the last decades and has lead to a loss of semi-natural habitats. These changes are likely to have affected both the composition and diversity of small mammal communities living in agricultural landscapes. In this context, we compared population abundance (expressed as an index of relative abundance), species richness (S), and species diversity (expressed as Shannon and Pielou indexes) of small mammal assemblages (i.e. sub-sets of the entire small mammal community) living in three areas in North-East Italy positioned along a gradient of agricultural land-use intensification (measured with the Landscape Conservation Index). We expected that assemblages would be less diverse and dominated by generalist species where the landscape was more intensely cultivated and where semi-natural habitats were less common. In the three areas, from a total of 4630 trap-nights, 668 individuals were captured with Sherman traps, belonging to four species (Apodemus agrarius, A. flavicollis, A. sylvaticus and Microtus arvalis). The results showed that population abundance, type of species present (but not species richness), and species diversity were affected by agricultural intensification and landscape naturalness. In particular, moving from less natural to more natural landscapes, we observed no effect on richness of species but increasing diversity due to a greater abundance of the more specialist species, such as A. agrarius and, partially, A. flavicollis, the latter only present in the most natural area. Generalist species, namely A. sylvaticus, and those associated with disturbed environments, such as M. arvalis, were instead more abundant in less natural landscapes. When considering population abundance, the highest overall abundance of small mammals was found in the most disturbed landscape. The results were consistent with those of research carried out in other agroecosystems of Europe and highlight the controversial effect of the anthropogenic impact on small mammal assemblages, since a decrease in species diversity may be associated with an increased overall population abundance, due to the success of few generalist species. \ua9 2014 Associazione Teriologica Italiana

FEEDING INTERACTION OF THE NON-NATIVE AFRICAN CATFISH (Clarias gariepinus BURCHELL, 1822) IN ITANHÉM RIVER ESTUARY, BAHIA, BRAZIL

A total of 214 stomachs of Clarias gariepinus, Centropomus undecimalis and C. parallelus from the Itanhém and Caravelas Rivers, northeastern Brazil, were analyzed to investigate the impact of the non-native species Clarias gariepinus on the Itanhém River food web as compared to that of the adjacent Caravelas River, where this species has not been registered. In Itanhém River, shrimp was the most important food for C. gariepinus, and Teleostei for C. parallelus. In the Caravelas River, Brachyura was the main food item for C. parallelus, and Teleostei for C. undecimalis. There was no food overlap between the species within or between rivers. There is no evidence, in the results of this study, of changes in the diet of the Centropomus parallelus due to the presence of the non-native species.Foram analisados 214 estômagos de Clarias gariepinus, Centropomus undecimalis e C. parallelus do rio Itanhém e rio Caravelas, nordeste do Brasil, com a finalidade de investigar o impacto da espécie exótica Clarias gariepinus sobre a trama trófica do Rio Itanhém, tendo como referência a alimentação das espécies nativas no Rio Caravelas. No Rio Itanhém, os camarões foram mais importantes na alimentação de Clarias gariepinus (55%), enquanto Teleostei (98,1%) foi para C. parallelus. Brachyura compôs 92,8% da dieta de C. parallelus do rio Caravelas, enquanto que para C. undecimalis, Teleostei compôs 72,5%. Não houve sobreposição alimentar em nenhum dos casos estudados. Pelos resultados desse trabalho não foi possível detectar indícios de mudanças na dieta de C. parallelus do Rio Itanhém

Direct Irradiation of Phenol and Para-Substituted Phenols with a Laser Pulse (266 nm) in Homogeneous and Micro-heterogeneous Media. A Time-Resolved Spectroscopy Study

Direct irradiation of para-substituted phenols under N2 atmosphere in homogeneous (cyclohexane, acetonitrile, and methanol) and micellar (SDS) solution was investigated by means of time-resolved spectroscopy. After a laser pulse (266 nm), two transient species were formed, viz. the para-substituted phenol radical-cations and the corresponding phenoxy radicals. The radical-cations showed a broad absorption band located between 390 and 460 nm, while the phenoxy radicals showed two characteristic bands centered at 320 nm and 400-410 nm. The deprotonation rate constant of radical-cations (kH) of 105 s-1 and the reaction rate constant of the phenoxy radicals (kR) in the order of 109-1010 M-1·s-1 have been derived. The kH rate constants gave good linear Hammett correlation with positive slope indicating that electron-withdrawing substituents enhance the radical-cation acidity. The binding constants (Kb) of the para-substituted phenols with the surfactant were also measured, and NOESY experiments showed that phenols were located in the hydrophobic core of the micelle. Finally, computational calculations provided the predicted absorption spectra of the transients and nice linear correlations were obtained between the theoretical and experimental energy of the lower absorption band of these species

Substituent and Surfactant Effects on the Photochemical Reaction of Some Aryl Benzoates in Micellar Green Environment^†

In this study, we carried out preparative and mechanistic studies on the photochemical reaction of a series of p-substituted phenyl benzoates in confined and sustainable micellar environment. The aim of this work is mainly focused to show whether the nature of the surfactant (ionic or nonionic) leads to noticeable selectivity in the photoproduct formation and whether the electronic effects of the substituents affect the chemical yields and the rate of formation of the 5-substituted-2-hydroxybenzophenone derivatives. Application of the Hammett linear free energy relationship (LFER) on the rate of formation of benzophenone derivatives, on the lower energy band of the UV-visible absorption spectra of the aryl benzoates and 5-substituted-2-hydroxybenzophenone derivatives allows a satisfactory quantification of the substituent effects. Furthermore, UV-visible and 2D-NMR (NOESY) spectroscopies have been employed to measure the binding constant Kb and the location of the aryl benzoates within the hydrophobic core of the micelle. Finally, TD-DFT calculations have been carried out to estimate the energies of the absorption bands of p-substituted phenyl benzoates and 5-substituted-2-hydroxybenzophenone derivatives providing good linear correlation with those values measured experimentally.Fil: Siano, Gastón. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Investigaciones en Hidratos de Carbono; ArgentinaFil: Crespi, Stefano. University of Groningen; Países BajosFil: Bonesi, Sergio Mauricio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Investigaciones en Hidratos de Carbono; Argentin

Photocatalytic fluoroalkylation reactions of organic compounds

Photocatalytic methods for fluoroalkyl-radical generation provide more convenient alternatives to the classical perfluoroalkyl-radical (Rf) production through chemical initiators, such as azo or peroxide compounds or the employment of transition metals through a thermal electron transfer (ET) initiation process. The mild photocatalytic reaction conditions tolerate a variety of functional groups and, thus, are handy to the late-stage modification of bioactive molecules. Transition metal-photocatalytic reactions for Rf radical generation profit from the redox properties of coordinatively saturated Ru or Ir organocomplexes to act as both electron donor and reductive species, thus allowing for the utilization of electron accepting and donating fluoroalkylating agents for Rf radical production. On the other hand, laboratory-available and inexpensive photoorgano catalysts (POC), in the absence of transition metals, can also act as electron exchange species upon excitation, resulting in ET reactions that produce Rf radicals. In this work, a critical account of transition metal and transition metal-free Rf radical production will be described with photoorgano catalysts, studying classical examples and the most recent investigations in the field.Fil: Barata Vallejo, Sebastian. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Química Orgánica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Bonesi, Sergio Mauricio. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Química Orgánica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Investigaciones en Hidratos de Carbono; ArgentinaFil: Postigo, Jose Alberto. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Química Orgánica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentin

Fluorination methods in drug discovery

Fluorination reactions of medicinal and biologically-active compounds will be discussed. Late stage fluorination strategies of medicinal targets have recently attracted considerable attention on account of the influence that the fluorine atom can impart to targets of medicinal importance, such as a modulation of lipophilicity, electronegativity, basicity and bioavailability, this latter as a consequence of membrane permeability. Therefore, the recourse to late-stage fluorine substitution on compounds with already known and relevant biological activity can provide the pharmaceutical industry with new leads with improved medicinal properties. The fluorination strategies will take into account different fluorinating reagents, nucleophilic, electrophilic and of radical nature. Diverse families of organic compounds such as (hetero)aromatic rings, and aliphatic substrates (sp3 , sp 2 , and sp carbon atoms) will be studied in late-stage fluorination reaction strategies.Fil: Yerien, Damián Emilio. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Química Orgánica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Bonesi, Sergio Mauricio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Investigaciones en Hidratos de Carbono; ArgentinaFil: Postigo, Jose Alberto. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Química Orgánica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentin

Selectivity in the photo-fries rearrangement of some aryl benzoates in green and sustainable media. Preparative and mechanistic studies

Irradiation of a series of p-substituted aryl 10 benzoates under N2 atmosphere in homogeneous and micellar 11 media was investigated by means of steady-state condition and 12 of time-resolved spectroscopy. A notable selectivity in favor of 13 the 2-hydroxybenzophenone derivatives was observed in 14 micellar media. The benzophenone derivatives were the 15 main photoproduct. On the other hand, in homogeneous 16 media (cyclohexane, acetonitrile, and methanol) the observed 17 product distribution was entirely different, viz. substituted 2- 18 hydroxybenzophenones, p-substituted phenols, benzyl and 19 benzoic acid were found. The binding constants in the 20 surfactant were also measured and NOESY experiments showed that the aryl benzoates were located in the hydrophobic core of 21 the micelle. Laser flash photolysis experiments led to the characterization of both p-substituted phenoxy radical and substituted 22 2-benzoylcyclohexadienone transients in homogeneous and micellar environment.Fil: Siano, Gastón. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Investigaciones en Hidratos de Carbono; ArgentinaFil: Crespi, Stefano. Universita Degli Studi Di Pavia; ItaliaFil: Mella, Mariella. Universita Degli Studi Di Pavia; ItaliaFil: Bonesi, Sergio Mauricio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Investigaciones en Hidratos de Carbono; Argentina. Universita Degli Studi Di Pavia; Itali