Electrospray ionization mass spectrometry analysis of changes in phospholipids in RBL-2H3 mastocytoma cells during degranulation

Biological membranes contain an extraordinary diversity of lipids. Phospholipids function as major structural elements of cellular membranes, and analysis of changes in the highly heterogeneous mixtures of lipids found in eukaryotic cells is central to understanding the complex functions in which lipids participate. Phospholipase-catalyzed hydrolysis of phospholipids often follows cell surface receptor activation. Recently, we demonstrated that granule fusion is initiated by addition of exogenous, nonmammalian phospholipases to permeabilized mast cells. To pursue this finding, we use positive and negative mode Fourier-transform ion cyclotron resonance mass spectrometry (FTICR-MS) to measure changes in the glycerophospholipid composition of total lipid extracts of intact and permeabilized RBL-2H3 (mucosal mast cell line) cells. The low energy of the electrospray ionization results in efficient production of molecular ions of phospholipids uncomplicated by further fragmentation, and changes were observed that eluded conventional detection methods. From these analyses we have spectrally resolved more than 130 glycerophospholipids and determined changes initiated by introduction of exogenous phospholipase C, phospholipase D, or phospholipase A2. These exogenous phospholipases have a preference for phosphatidylcholine with long polyunsaturated alkyl chains as substrates and, when added to permeabilized mast cells, produce multiple species of mono- and polyunsaturated diacylglycerols, phosphatidic acids, and lysophosphatidylcholines, respectively. The patterns of changes of these lipids provide an extraordinarily rich source of data for evaluating the effects of specific lipid species generated during cellular processes, such as exocytosis.

Intermolecular and Intramolecular Charge Transfer in Functional Molecular Materials

This thesis is devoted to the investigation of inter and intramolecular charge transfer (CT) in molecular functional materials and specifically organic dyes and CT crystals. An integrated approach encompassing quantum-chemical calculations, semiempirical tools, theoretical models and spectroscopic measurements is applied to understand structure-property relationships governing the low-energy physics of these materials. Four main topics were addressed: 1) Spectral properties of organic dyes. Charge-transfer dyes are constituted by electron donor (D) and electron acceptor (A) units linked through bridge(s) to form molecules with different symmetry and dimensionality. Their low-energy physics is governed by the charge resonance between D and A groups and is effectively described by a family of parametric Hamiltonians known as essential-state models. These models account for few electronic states, corresponding to the main resonance structures of the relevant dye, leading to a simple picture that is completed introducing the coupling of the electronic system to molecular vibrations, treated in a non-adiabatic way, and an effective classical coordinate, describing polar solvation. In this work a specific essential-state model was proposed and parametrized for the dye Brilliant Green. The central issue in this work has been the definition of the diabatic states, a not trivial task for a multi-branched chromophore. In a second effort, we have used essential-state models for the description of the early-stage dynamics of excited states after ultrafast excitation. Crucial to this work is the fully non-adiabatic treatment of the coupled electronic and vibrational motion, allowing for a reliable description of the dynamics of systems showing a multistable, broken-symmetry excited state. 2) Mixed-stack CT salts. Mixed-stack (MS) CT crystals are an interesting class of multifunctional molecular materials, where D and A molecules arrange themselves to form stacks, leading to delocalized electrons in one dimension. The interplay between the intermolecular CT, electrostatic interactions, lattice phonons and molecular vibrations leads to intriguing physical properties that include (photoinduced) phase transitions, multistability, antiferromagnetism, ferroelectricity and potential multiferroicity. The standard microscopic model to describe this family of materials is the Modified Hubbard model accounting for electron-phonon coupling (Peierls coupling), electron-molecular vibrations coupling (Holstein coupling) and electrostatic interactions. We adopt and validate a method, based on DFT calculations on dimeric DA structures, to extract relevant model parameters. The approach offers a powerful tool to shed light on the complex physics of MS-CT salts. 3) Charge transfer in organic radical dipolar dyes. In collaboration with the group of Prof. Jaume Veciana (ICMAB- Barcellona), we have studied spectral properties of a special class of CT dyes with D-bridge-A structure where the acceptor group is a stable radical (of the perchlorotriphenylmethyl, PTM, family), leading to an open-shell CT dyes. These materials are of interest since they associate the electronic and optical properties of CT dyes with magnetic properties from the unpaired electron. The first effort was devoted to the parametrization of the relevant essential-state model. Two strategies were adopted, one based on the calculation of the low-energy spectral properties, the other based on the variation of ground state properties with an applied electric field. 4) The spectral properties of organic nanoparticles based on radical species are investigated in collaboration with Dr. I. Ratera (ICMAB- Barcellona). Intriguing spectroscopic behavior was observed pointing to the presence of excimer states. In an attempt to rationalize these findings, extensive calculations (TD-DFT and ZINDO) were performed. The results for the isolated dyes are validated against experimental spectra in solution. To address intermolecular interactions we studied dimeric structures in the gas phase, but the preliminary results obtained do not support excimer formation.

Experimental and theoretical cross sections for positron scattering from the pentane isomers.

Isomerism is ubiquitous in chemistry, physics, and biology. In atomic and molecular physics, in particular, isomer effects are well known in electron-impact phenomena; however, very little is known for positron collisions. Here we report on a set of experimental and theoretical cross sections for low-energy positron scattering from the three structural isomers of pentane: normal-pentane, isopentane, and neopentane. Total cross sections for positron scattering from normal-pentane and isopentane were measured at the University of Trento at incident energies between 0.1 and 50 eV. Calculations of the total cross sections, integral cross sections for elastic scattering, positronium formation, and electronic excitations plus direct ionization, as well as elastic differential cross sections were computed for all three isomers between 1 and 1000 eV using the independent atom model with screening corrected additivity rule. No definitive evidence of a significant isomer effect in positron scattering from the pentane isomers appears to be present. (C) 2016 AIP Publishing LLC.

Architecture of a Bench-Type Carbonate Lake Margin and Its Relation to Fluvially Dominated Deltas, Las Minas Basin, Upper Miocene, Spain

The Upper Miocene stratigraphic succession of the Las Minas Basin, located at the external zone of the Betic Chain in SE Spain, preserves several examples of lake carbonate bench deposits. Excellent exposures of the carbonate benches allow detailed observation of the architecture of these sediments and provide new insights for the ‘‘steep-gradient bench margin–low energy’’ model proposed by Platt and Wright (1991). The lake carbonate benches developed in close association with fluvially dominated shallow deltas that exhibit typical Gilbert-type profiles. The delta sequences comprise bottomset prodelta marl facies, distal to proximal foreset facies, deposited mainly in a delta-front environment, and topset facies, the latter reflecting both subaqueous delta-front and subaerial delta-plain environments. The development of the carbonate benches was constrained by the convexupward morphology of the deltaic deposits, which led to the available accommodation space for the growth of the steep-gradient platforms. The benches display a progradational pattern characterized by sigmoid-oblique internal geometries and offlap upper boundary relationships, which suggests that the carbonate benches developed under slow though continuous lake-level rise. Both the dimensions of the benches and the dominant carbonate components (i.e., encrusted charophyte stems and calcified cyanobaterial remains), allow comparisons with the progradational marl benches recognized in modern temperate hardwater lakes. Accordingly, the case study presented here provides a good ancient sedimentary analog for low-energy lake carbonate benches. Moreover, the evolutionary trend inferred from the fossil example offers new insights into the depositional conditions of this type of sediment and allows recognition of the transitional pattern from bench to ramp carbonate lake margins.

Pseudoscalar susceptibilities and quark condensates: chiral restoration and lattice screening masses

We derive the formal Ward identities relating pseudoscalar susceptibilities and quark condensates in three-flavor QCD, including consistently the 77-n' sector and the U-A(1) anomaly. These identities are verified in the low-energy realization provided by ChPT, both in the standard SU(3) framework for the octet case and combining the use of the SU(3) framework and the large-Nc expansion of QCD to account properly for the nonet sector and anomalous contributions. The analysis is performed including finite temperature corrections as well as the calculation of U(3) quark condensates and all pseudoscalar susceptibilities, which together with the full set of Ward identities, are new results of this work. Finally, the Ward identities are used to derive scaling relations for pseudoscalar masses which explain the behavior with temperature of lattice screening masses near chiral symmetry restoration.

Fabricação e caracterização de detector de Barreira de superfície a partir de substrato de silício comercial

Neste trabalho foram desenvolvidos detectores de radiação Barreira de superfície de silício que fossem capazes de detectar a presença da radiação gama de baixa energia proveniente de sementes de iodo-125 utilizada em tratamentos de braquiterapia. A partir de substratos comerciais de silício foram desenvolvidos os detectores, de uma sequência que partiu de tratamentos químicos nas superfícies destes substratos com a intenção de minimizar os possíveis ruídos gerados, validação das amostras obtidas como diodos, assegurando características detectoras, e a efetiva utilização como detector para fontes radioativas de iodo-125 com energia em torno de 25 kev e amerício-251 com energia na ordem de 59 kev. Finalizou realizando a análise dos espectros de energia obtidos e assim foi possível observar a capacidade destes detectores para mensuração da energia proveniente destas sementes.

Reações fotoinduzidas em alguns complexos de rênio e desenvolvimento de dispositivos moleculares

Neste trabalho foi realizado o estudo do comportamento fotoquímico e fotofísico de complexos mononucleares de rênio do tipo fac-[Re(CO)3(N N)(L)]+(N N = 1,10-fenantrolina, phen, dipirido[3,2-a:2,3-c]fenazina, dppz, L= trans-1,2bis(4-piridil)etileno, trans-bpe, trans-4-estirilpiridina. trans-stpy) e dos complexos binucleares [(CO)3(phen)Re(trans-bpe)Re(phen)(CO)3]2+, [(CO)3(phen)Re(trans-bpe)Fe(CN5]2- e [(phen)(CO)3Re(trans-bpe)Os(terpy)(bpy)]3+. O enfoque principal deste trabalho é a investigação das propriedades fotoquímicas dos complexos fac-[ Re(CO)3(phen)(trans-bpe)]+, fac-[Re(CO)3(phen)(trans-stpy)]+ fac-[Re(CO)3(dppz)(trans-bpe)+ e [(CO)3(phen)Re(trans-bpe)Re(phen)(CO)3]2+. Observou-se que os compostos em solução de acetonitrila, sob irradiação a 313, 334 ou 365 nm, apresentam variação espectral com definição de pontos isosbésticos, resultante do processo de fotoisomerização trans→cis do ligante coordenado trans-piridil etileno. Os rendimentos quânticos, Φ, da reação de fotoisomerização foram calculados com base no decaimento espectral das bandas de absorção das transições eletrônicas. Os valores médios determinados para a fotoisomeriação dos complexos em solução de CH3CN variam de 0,15 - 0,39 sob excitação a 313 nm e de 0,12 - 0,33 sob excitação a 365 nm. As reações de fotoisomerização foram monitoradas também por medidas de emissão e por RMN de 1H. Observou-se um aumento da intensidade de luminescência com o tempo de irradiação dos complexos, consistente com o estado emissivo 3MLCT dπ[(Re)→π*(α-diimina). Após irradiação, as reações de fotoisomerização dos complexos foram monitoradas por RMN de 1H. Os sinais de prótons do isômero trans tiveram um decréscimo gradual, enquanto que a intensidade dos sinais referentes aos prótons da espécie cis aumentaram. Os rendimentos quânticos para o processo de fotoisomerização dos complexos foram calculados através da integração das áreas dos sinais de prótons. Os valores obtidos foram maiores, pelo menos o dobro, que aqueles valores obtidos via espectroscopia UV-Vis. O comportamento fotoquímico dos complexos incorporados em polimetacrilato de metila, PMMA, foi também investigado. A fotólise cios complexos em filmes de PMMA conduz à variação espectral, de absorção e emissão, similar àquela observada em solução de acetonitrila, atribuícla ao processo de fotoisomerização trans → cis do ligante coordenado. Este estudo mostra que a fotoisomerização do ligante coordenado trans-piridil etileno pode ser promovida também em meio rígido. Essa característica. típica de um dispositivo molecular, pode ser convenientemente explorada no desenvolvimento de fotossensores. As medidas de TRIR mostram que o estado excitado de menor energia para o fac-[Re(CO)3(phen)(trans-bpe)+ é o 3ππ*. Para o fac-[Re(CO)3(phen)(cis-bpe)]+ a ordem dos estados excitados aparecem invertidas com o 3MLCT <3ππ*, evidenciado pela emissão do complexo cis à temperatura ambiente. Nas espécies binucleares, [(phen) Re(CO)3(trans-bpe)Os(terpy)(bpy)]3+ e [(CO)3(phen)Re(trans-bpe)Fe(CN)5]2-, a fotoisomerização trans → cis do ligante coordenado trans-bpe, característica da subunidade fac-[Re(CO)3(phen)(trans-bpe)]+, é inibida pela competição de transferência de energia intramolecular. Em meio rígido, em PMMA ou em EPA a 77 K, os máximos de emissão dos complexos fac-[Re(CO)3(phen)(cis-bpe)]+, fac-[Re(CO)3(phen)(cis-stpy)r e [(CO)3(phen)Re(cis-bpe)Re(phen)(CO)3]2+ sofrem um deslocamento hipsocrômico com o aumento da rigidez do meio. As mudanças nas propriedades emissivas, em termos de energia e tempo de vida do estado excitado, são discutidas baseadas no efeito rigidocrômico luminescente. O trabalho mostra uma forma interessante de fotos sensibilizar um substrato orgâmco usando o fato de que a coordenação estende a absorção do ligante a uma região de comprimento de onda maior e promove a fotoisomerização assistida por complexos metálicos em energias menores.

Critical behavior of su(1|1) supersymmetric spin chains with long-range interactions

We introduce a general class of su(1|1) supersymmetric spin chains with long-range interactions which includes as particular cases the su(1|1) Inozemtsev (elliptic) and Haldane-Shastry chains, as well as the XX model. We show that this class of models can be fermionized with the help of the algebraic properties of the su(1|1) permutation operator and take advantage of this fact to analyze their quantum criticality when a chemical potential term is present in the Hamiltonian. We first study the low-energy excitations and the low-temperature behavior of the free energy, which coincides with that of a (1+1)-dimensional conformal field theory (CFT) with central charge c=1 when the chemical potential lies in the critical interval (0,E(π)), E(p) being the dispersion relation. We also analyze the von Neumann and Rényi ground state entanglement entropies, showing that they exhibit the logarithmic scaling with the size of the block of spins characteristic of a one-boson (1+1)-dimensional CFT. Our results thus show that the models under study are quantum critical when the chemical potential belongs to the critical interval, with central charge c=1. From the analysis of the fermion density at zero temperature, we also conclude that there is a quantum phase transition at both ends of the critical interval. This is further confirmed by the behavior of the fermion density at finite temperature, which is studied analytically (at low temperature), as well as numerically for the su(1|1) elliptic chain.

Fermi-edge singularities in linear and nonlinear ultrafast spectroscopy

We discuss Fermi-edge singularity effects on the linear and nonlinear transient response of an electron gas in a doped semiconductor. We use a bosonization scheme to describe the low-energy excitations, which allows us to compute the time and temperature dependence of the response functions. Coherent control of the energy absorption at resonance is analyzed in the linear regime. It is shown that a phase shift appears in the coherent control oscillations, which is not present in the excitonic case. The nonlinear response is calculated analytically and used to predict that four wave-mixing experiments would present a Fermi-edge singularity when the exciting energy is varied. A new dephasing mechanism is predicted in doped samples that depends linearly on temperature and is produced by the low-energy bosonic excitations in the conduction band.

Role of potassium orbitals in the metallic behavior of K3picene

Detailed electronic structure calculations of picene clusters doped by potassium modeling the crystalline K3picene structure show that while two electrons are completely transferred from potassium atoms to the lowest-energy unoccupied molecular orbital of pristine picene, the third one remains closely attached to both material components. Multiconfigurational analysis is necessary to show that many structures of almost degenerate total energies compete to define the cluster ground state. Our results prove that the 4s orbital of potassium should be included in any interaction model describing the material. We propose a quarter-filled two-orbital model as the most simple model capable of describing the electronic structure of K-intercalated picene. Precise solutions obtained by a development of the Lanczos method show low-energy electronic excitations involving orbitals located at different positions. Consequently, metallic transport is possible in spite of the clear dominance of interaction over hopping.

Integrated taphonomy in an open-marine platform: The Lower Cretaceous of Sierra Helada (Betic Cordillera, SE Spain)

A detailed taphonomic analysis was carried out on the lower Albian deposits of the Sierra Helada section (Alicante, Betic Cordillera, southeastern Spain). Ten taphonomic characters were studied and ten skeletal concentrations were defined on the basis of taphonomic features and the dominant taxa. Cluster analysis was performed on the dataset represented by the abundance of the taphonomic characters in each skeletal concentration. This enabled the definition of four different taphonomic categories: 1) skeletal concentrations characterized by the presence of fossils preserved in life position, 2) skeletal concentrations showing very little physical reworking, 3) skeletal concentrations related to high-energy background conditions, and 4) skeletal concentrations produced by medium- to high-energy events. Four taphofacies were defined on the basis of the main sedimentological features and the most representative skeletal concentrations. Taphofacies A represents the low energy outer platform, rich in skeletal concentrations with echinoids in life position and only slightly reworked. The second taphofacies (taphofacies B) is very rich in reworked echinoid tests and calcarenitic beds and records the transition to shallower areas, while taphofacies C shows abundant thick-bedded calcarenites and skeletal concentrations produced by sediment transport and rapid deposition. Finally, cross-bedded grainstone beds, which are rich in fine-grained fragmented, locally reoriented bioclasts (taphofacies D), record the existence of shifting sandy dunes in the shallow inner part of the platform.

Orbital phase-resolved spectroscopy of 4U 1538−52 with MAXI

Context. 4U 1538−52, an absorbed high mass X-ray binary with an orbital period of ~3.73 days, shows moderate orbital intensity modulations with a low level of counts during the eclipse. Several models have been proposed to explain the accretion at different orbital phases by a spherically symmetric stellar wind from the companion. Aims. The aim of this work is to study both the light curve and orbital phase spectroscopy of this source in the long term. In particular, we study the folded light curve and the changes in the spectral parameters with orbital phase to analyse the stellar wind of QV Nor, the mass donor of this binary system. Methods. We used all the observations made from the Gas Slit Camera on board MAXI of 4U 1538−52 covering many orbits continuously. We obtained the good interval times for all orbital phase ranges, which were the input for extracting our data. We estimated the orbital period of the system and then folded the light curves, and we fitted the X-ray spectra with the same model for every orbital phase spectrum. We also extracted the averaged spectrum of all the MAXI data available. Results. The MAXI spectra in the 2–20 keV energy range were fitted with an absorbed Comptonisation of cool photons on hot electrons. We found a strong orbital dependence of the absorption column density but neither the fluorescence iron emission line nor low energy excess were needed to fit the MAXI spectra. The variation in the spectral parameters over the binary orbit were used to examine the mode of accretion onto the neutron star in 4U 1538−52. We deduce a best value of Ṁ/v∞ = 0.65 × 10-9M⊙ yr-1/ (km s-1) for QV Nor.

Design of Activated Carbon/Activated Carbon Asymmetric Capacitors

Supercapacitors are energy storage devices that offer a high power density and a low energy density in comparison with batteries. Their limited energy density can be overcome by using asymmetric configuration in mass electrodes, where each electrode works within their maximum available potential window, rendering the maximum voltage output of the system. Such asymmetric capacitors are optimized using the capacitance and the potential stability limits of the electrodes, with the reliability of the design largely depending on the accuracy and the approach taken for the electrochemical characterization. Therefore, the performance could be lower than expected and even the system could break down, if a well thought out procedure is not followed. In this work, a procedure for the development of asymmetric supercapacitors based on activated carbons is detailed. Three activated carbon materials with different textural properties and surface chemistry have been systematically characterized in neutral aqueous electrolyte. The asymmetric configuration of the masses of both electrodes in the supercapacitor has allowed to cover a higher potential window, resulting in an increase of the energy density of the three devices studied when compared with the symmetric systems, and an improved cycle life.

Derivation of the spin Hamiltonians for Fe in MgO

A method to calculate the effective spin Hamiltonian for a transition metal impurity in a non-magnetic insulating host is presented and applied to the paradigmatic case of Fe in MgO. In the first step we calculate the electronic structure employing standard density functional theory (DFT), based on generalized gradient approximation (GGA), using plane waves as a basis set. The corresponding basis of atomic-like maximally localized Wannier functions is derived and used to represent the DFT Hamiltonian, resulting in a tight-binding model for the atomic orbitals of the magnetic impurity. The third step is to solve, by exact numerical diagonalization, the N electron problem in the open shell of the magnetic atom, including both effects of spin–orbit and Coulomb repulsion. Finally, the low energy sector of this multi-electron Hamiltonian is mapped into effective spin models that, in addition to the spin matrices S, can also include the orbital angular momentum L when appropriate. We successfully apply the method to Fe in MgO, considering both the undistorted and Jahn–Teller (JT) distorted cases. Implications for the influence of Fe impurities on the performance of magnetic tunnel junctions based on MgO are discussed.

(Table 3) Textural and bulk mineralogy of Pliocene and Pleistocene sediments from ODP Hole 161-976B

The Pliocene and Pleistocene deposits recovered at Site 976 from the northwestern Alboran Sea at the Málaga base-of-slope include five main sedimentary facies: hemipelagic, turbidite, homogeneous gravity-flow, contourite, and debris-flow facies. The thickness and vertical distribution of these facies into lithostratigraphic Units I, II, and III show that the turbidites and hemipelagic facies are the dominant associations. The Pliocene and Pleistocene depositional history has been divided into three sedimentary stages: Stage I of early Pliocene age, in which hemipelagic and low-energy turbidites were the dominant processes; Stage II of early Pleistocene/late Pliocene age, in which the dominant processes were the turbidity currents interrupted by short episodes of other gravity flows (debris-flows and homogeneous gravity-flow facies) and bottom currents; and Stage III of Pleistocene age, in which both hemipelagic and low-energy gravity-flow processes occurred. The sedimentation during these three stages was controlled mainly by sea-level changes and also by the sediment supply that caused rapid terrigenous sedimentation variations from a proximal source represented by the Fuengirola Canyon.