A calcareous nannofossil and organic geochemical study of marine palaeoenvironmental changes across the Sinemurian/Pliensbachian (early Jurassic, ~191Ma) in Portugal

The Sinemurian/Pliensbachian boundary (~ 191 Ma) is acknowledged as one of the most important steps in the radiation of planktonic organisms, especially primary producers such as dinoflagellates and coccolithophores. To date, there is no detailed study documenting changes in planktonic assemblages related to palaeoceanographic changes across this boundary. The aim of this study is to characterize the palaeoenvironmental changes occurring across the Sinemurian/Pliensbachian boundary at the São Pedro de Moel section (Lusitanian Basin, Portugal) using micropalaeontology and organic geochemistry approaches. Combined calcareous nannofossil assemblage and lipid biomarker data document for a decrease in primary productivity in relation to a major sea-level rise occurring above the boundary. The Lusitanian Basin was particularly restricted during the late Sinemurian with a relatively low sea level, a configuration that led to the recurrent development of black shales. After a sharp sea-level fall, the basin became progressively deeper and more open during the earliest Pliensbachian, subsequently to a major transgression. This sea-level increase seems to have been a global feature and could have been related to the opening of the Hispanic Corridor that connected the Tethys and palaeo-Pacific oceans. The palaeoceanographic and palaeoclimatic changes induced by this opening may have played a role in the diversification of coccolithophores with the first occurrence or colonization of Tethyan waters by placolith-type coccoliths

Dissecting the supramolecular dispersion of fullerenes by proteins/peptides: Amino acid ranking and driving forces for binding to c60

Molecular dynamics simulations were used to quantitatively investigate the interactions between the twenty proteinogenic amino acids and C60. The conserved amino acid backbone gave a constant energetic interaction ~5.4 kcal mol−1, while the contribution to the binding due to the amino acid side chains was found to be up to ~5 kcal mol−1 for tryptophan but lower, to a point where it was slightly destabilizing, for glutamic acid. The effects of the interplay between van der Waals, hydrophobic, and polar solvation interactions on the various aspects of the binding of the amino acids, which were grouped as aromatic, charged, polar and hydrophobic, are discussed. Although π–π interactions were dominant, surfactant‐like and hydrophobic effects were also observed. In the molecular dynamics simulations, the interacting residues displayed a tendency to visit configura-tions (i.e., regions of the Ramachandran plot) that were absent when C60 was not present. The amino acid backbone assumed a “tepee‐like” geometrical structure to maximize interactions with the fullerene cage. Well‐defined conformations of the most interactive amino acids (Trp, Arg, Met) side chains were identified upon C60 binding

The peculiar herpetofauna of some Tsaratanana rainforests and its affinities with Manongarivo and other massifs and forests of northern Madagascar

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Dissecting the Interactions between Chlorin e6 and Human Serum Albumin

Chlorin e6 (Ce6) is among the most used sensitizers in photodynamic (PDT) and sonodynamic (SDT) therapy; its low solubility in water, however, hampers its clinical exploitation. Ce6 has a strong tendency to aggregate in physiological environments, reducing its performance as a photo/sono-sensitizer, as well as yielding poor pharmacokinetic and pharmacodynamic properties. The interaction of Ce6 with human serum albumin (HSA) (i) governs its biodistribution and (ii) can be used to improve its water solubility by encapsulation. Here, using ensemble docking and microsecond molecular dynamics simulations, we identified the two Ce6 binding pockets in HSA, i.e., the Sudlow I site and the heme binding pocket, providing an atomistic description of the binding. Comparing the photophysical and photosensitizing properties of Ce6@HSA with respect to the same properties regarding the free Ce6, it was observed that (i) a red-shift occurred in both the absorption and emission spectra, (ii) a maintaining of the fluorescence quantum yield and an increase of the excited state lifetime was detected, and (iii) a switch from the type II to the type I mechanism in a reactive oxygen species (ROS) production, upon irradiation, took place

Light-Enhanced Cytotoxicity of Doxorubicin by Photoactivation

The combination of photodynamic therapy with chemotherapy (photochemotherapy, PCT) can lead to additive or synergistic antitumor effects. Usually, two different molecules, a photosensitizer (PS) and a chemotherapeutic drug are used in PCT. Doxorubicin is one of the most successful chemotherapy drugs. Despite its high efficacy, two factors limit its clinical use: severe side effects and the development of chemoresistance. Doxorubicin is a chromophore, able to absorb light in the visible range, making it a potential PS. Here, we exploited the intrinsic photosensitizing properties of doxorubicin to enhance its anticancer activity in leukemia, breast, and epidermoid carcinoma cells, upon irradiation. Light can selectively trigger the local generation of reactive oxygen species (ROS), following photophysical pathways. Doxorubicin showed a concentration-dependent ability to generate peroxides and singlet oxygen upon irradiation. The underlying mechanisms leading to the increase in its cytotoxic activity were intracellular ROS generation and the induction of necrotic cell death. The nuclear localization of doxorubicin represents an added value for its use as a PS. The use of doxorubicin in PCT, simultaneously acting as a chemotherapeutic agent and a PS, may allow (i) an increase in the anticancer effects of the drug, and (ii) a decrease in its dose, and thus, its dose-related adverse effects

Quantum non-equilibrium dynamics of Rydberg gases in the presence of dephasing noise of different strengths

In the presence of strong dephasing noise the dynamics of Rydberg gases becomes effectively classical, due to the rapid decay of quantum superpositions between atomic levels. Recently a great deal of attention has been devoted to the stochastic dynamics that emerges in that limit, revealing several interesting features, including kinetically constrained glassy behaviour, self-similarity and aggregation effects. However, the non-equilibrium physics of these systems, in particular in the regime where coherent and dissipative processes contribute on equal footing, is yet far from being understood. To explore this we study the dynamics of a small one-dimensional Rydberg lattice gas subject to dephasing noise by numerically integrating the quantum master equation. We interpolate between the coherent and the strongly dephased regime by defining a generalised concept of a blockade length. We find indications that the main features observed in the strongly dissipative limit persist when the dissipation is not strong enough to annihilate quantum coherences at the dynamically relevant time scales. These features include the existence of a time-dependent Rydberg blockade radius, and a growth of the density of excitations which is compatible with the power-law behaviour expected in the classical limit

Low energy high angular resolution neutral atom detection by means of micro-shuttering techniques: the BepiColombo SERENA/ELENA sensor

The neutral sensor ELENA (Emitted Low-Energy Neutral Atoms) for the ESA cornerstone BepiColombo mission to Mercury (in the SERENA instrument package) is a new kind of low energetic neutral atoms instrument, mostly devoted to sputtering emission from planetary surfaces, from E ~20 eV up to E~5 keV, within 1-D (2x76 deg). ELENA is a Time-of-Flight (TOF) system, based on oscillating shutter (operated at frequencies up to a 100 kHz) and mechanical gratings: the incoming neutral particles directly impinge upon the entrance with a definite timing (START) and arrive to a STOP detector after a flight path. After a brief dissertation on the achievable scientific objectives, this paper describes the instrument, with the new design techniques approached for the neutral particles identification and the nano-techniques used for designing and manufacturing the nano-structure shuttering core of the ELENA sensor. The expected count-rates, based on the Hermean environment features, are shortly presented and discussed. Such design technologies could be fruitfully exported to different applications for planetary exploration.Comment: 11 page