Study of molecules of astrochemical, astrophysical and atmospheric interest by means of High - Resolution Infrared Spectroscopy

The spectroscopic investigation of the gas-phase molecules relevant for the chemistry of the atmosphere and of the interstellar medium has been performed. Two types of molecules have been studied, linear and symmetric top. Several experimental high-resolution techniques have been adopted, exploiting the spectrometers available in Bologna, Venezia, Brussels and Wuppertal: Fourier-Transform-Infrared Spectroscopy, Cavity-Ring-Down Spectroscopy, Cavity-Enhanced-Absorption Spectroscopy, Tunable-Diode-Laser Spectroscopy. Concerning linear molecules, the spectra of a number of isotopologues of acetylene, 12C2D2, H12C13CD, H13C12CD, 13C12CD2, of DCCF and monodeuterodiacetylene DC4H, have been studied, from 320 to 6800 cm-1. This interval covers bending, stretching, overtone and combination bands, the focus on specific ranges depending on the molecule. In particular, the analysis of the bending modes has been performed for 12C2D2 (450-2200 cm-1), 13C12CD2 (450-1700 cm-1), DCCF (320-850cm-1) and DC4H (450-1100 cm-1), of the stretching-bending system for 12C2D2 (450-5500 cm-1) and of the 2nu1 and combination bands up to four quanta of excitation for H12C13CD, H13C12CD and 13C12CD2 (6130-6800 cm-1). In case of symmetric top molecules, CH3CCH has been investigated in the 2nu1 region (6200-6700 cm-1), which is particularly congested due to the huge network of states affected by Coriolis and anharmonic interactions. The bending fundamentals of 15ND3 (450-2700 cm-1) have been studied for the first time, characterizing completely the bending states, v2 = 1 and v4 = 1, whereas the analysis of the stretching modes, which evidenced the presence of several perturbations, has been started. Finally, the fundamental band nu4 of CF3Br in the 1190-1220 cm-1 region has been investigated. Transitions belonging to the CF379Br and CF381Br molecules have been identified since the spectra were recorded using a sample containing the two isotopologues in natural abundance. This allowed the characterization of the v4 = 1 state for both isotopologues and the evaluation of the bromine isotopic splitting.

Galactic fountain flows in high-resolution hydrodynamical simulations of galaxy disks

Feedback from the most massive components of a young stellar cluster deeply affects the surrounding ISM driving an expanding over-pressured hot gas cavity in it. In spiral galaxies these structures may have sufficient energy to break the disk and eject large amount of material into the halo. The cycling of this gas, which eventually will fall back onto the disk, is known as galactic fountains. We aim at better understanding the dynamics of such fountain flow in a Galactic context, frame the problem in a more dynamic environment possibly learning about its connection and regulation to the local driving mechanism and understand its role as a metal diffusion channel. The interaction of the fountain with a hot corona is hereby analyzed, trying to understand the properties and evolution of the extraplanar material. We perform high resolution hydrodynamical simulations with the moving-mesh code AREPO to model the multi-phase ISM of a Milky Way type galaxy. A non-equilibrium chemical network is included to self consistently follow the evolution of the main coolants of the ISM. Spiral arm perturbations in the potential are considered so that large molecular gas structures are able to dynamically form here, self shielded from the interstellar radiation field. We model the effect of SN feedback from a new-born stellar cluster inside such a giant molecular cloud, as the driving force of the fountain. Passive Lagrangian tracer particles are used in conjunction to the SN energy deposition to model and study diffusion of freshly synthesized metals. We find that both interactions with hot coronal gas and local ISM properties and motions are equally important in shaping the fountain. We notice a bimodal morphology where most of the ejected gas is in a cold $10^4$ K clumpy state while the majority of the affected volume is occupied by a hot diffuse medium. While only about 20\% of the produced metals stay local, most of them quickly diffuse through this hot regime to great scales.

CH4, CO, and H2O spectroscopy for the Sentinel-5 Precursor mission: an assessment with the Total Carbon Column Observing Network measurements

The TROPOspheric Monitoring Instrument (TROPOMI) will be part of ESA's Sentinel-5 Precursor (S5P) satellite platform scheduled for launch in 2015. TROPOMI will monitor methane and carbon monoxide concentrations in the Earth's atmosphere by measuring spectra of back-scattered sunlight in the short-wave infrared (SWIR). S5P will be the first satellite mission to rely uniquely on the spectral window at 4190–4340 cm−1 (2.3 μm) to retrieve CH4 and CO. In this study, we investigated if the absorption features of the three relevant molecules CH4, CO, and H2O are adequately known. To this end, we retrieved total columns of CH4, CO, and H2O from absorption spectra measured by two ground-based Fourier transform spectrometers that are part of the Total Carbon Column Observing Network (TCCON). The retrieval results from the 4190–4340 cm−1 range at the TROPOMI resolution (0.45 cm−1) were then compared to the CH4 results obtained from the 6000 cm−1 region, and the CO results obtained from the 4190–4340 cm−1 region at the higher TCCON resolution (0.02 cm−1). For TROPOMI-like settings, we were able to reproduce the CH4 columns to an accuracy of 0.3% apart from a constant bias of 1%. The CO retrieval accuracy was, through interference, systematically influenced by the shortcomings of the CH4 and H2O spectroscopy. In contrast to CH4, the CO column error also varied significantly with atmospheric H2O content. Unaddressed, this would introduce seasonal and latitudinal biases to the CO columns retrieved from TROPOMI measurements. We therefore recommend further effort from the spectroscopic community to be directed at the H2O and CH4 spectroscopy in the 4190–4340 cm−1 region.

Approximate decoding approaches for network coded correlated data

This paper considers a framework where data from correlated sources are transmitted with the help of network coding in ad hoc network topologies. The correlated data are encoded independently at sensors and network coding is employed in the intermediate nodes in order to improve the data delivery performance. In such settings, we focus on the problem of reconstructing the sources at decoder when perfect decoding is not possible due to losses or bandwidth variations. We show that the source data similarity can be used at decoder to permit decoding based on a novel and simple approximate decoding scheme. We analyze the influence of the network coding parameters and in particular the size of finite coding fields on the decoding performance. We further determine the optimal field size that maximizes the expected decoding performance as a trade-off between information loss incurred by limiting the resolution of the source data and the error probability in the reconstructed data. Moreover, we show that the performance of the approximate decoding improves when the accuracy of the source model increases even with simple approximate decoding techniques. We provide illustrative examples showing how the proposed algorithm can be deployed in sensor networks and distributed imaging applications.

A high-resolution map of direct and indirect connectivity of erosion risk areas to surface waters in Switzerland: A risk assessment tool for planning and policy-making

Off-site effects of soil erosion are becoming increasingly important, particularly the pollution of surface waters. In order to develop environmentally efficient and cost effective mitigation options it is essential to identify areas that bear both a high erosion risk and high connectivity to surface waters. This paper introduces a simple risk assessment tool that allows the delineation of potential critical source areas (CSA) of sediment input into surface waters concerning the agricultural areas of Switzerland. The basis are the erosion risk map with a 2 m resolution (ERM2) and the drainage network, which is extended by drained roads, farm tracks, and slope depressions. The probability of hydrological and sedimentological connectivity is assessed by combining soil erosion risk and extended drainage network with flow distance calculation. A GIS-environment with multiple-flow accumulation algorithms is used for routing runoff generation and flow pathways. The result is a high resolution connectivity map of the agricultural area of Switzerland (888,050 ha). Fifty-five percent of the computed agricultural area is potentially connected with surface waters, 45% is not connected. Surprisingly, the larger part of 34% (62% of the connected area) is indirectly connected with surface waters through drained roads, and only 21% are directly connected. The reason is the topographic complexity and patchiness of the landscape due to a dense road and drainage network. A total of 24% of the connected area and 13% of the computed agricultural area, respectively, are rated with a high connectivity probability. On these CSA an adapted land use is recommended, supported by vegetated buffer strips preventing sediment load. Even areas that are far away from open water bodies can be indirectly connected and need to be included in planning of mitigation measures. Thus, the connectivity map presented is an important decision-making tool for policy-makers and extension services. The map is published on the web and thus available for application.

Southern Hemisphere high-resolution palaeoclimate records of the last 2000 years

This study presents a comprehensive assessment of high-resolution Southern Hemisphere (SH) paleoarchives covering the last 2000 years. We identified 174 monthly to annually resolved climate proxy (tree ring, coral, ice core, documentary, speleothem and sedimentary) records from the Hemisphere. We assess the interannual and decadal sensitivity of each proxy record to large-scale circulation indices from the Pacific, Indian and Southern Ocean regions over the twentieth century. We then analyse the potential of this newly expanded palaeoclimate network to collectively represent predictands (sea surface temperature, sea level pressure, surface air temperature and precipitation) commonly used in climate reconstructions. The key dynamical centres-of-action of the equatorial Indo-Pacific are well captured by the palaeoclimate network, indicating that there is considerable reconstruction potential in this region, particularly in the post AD 1600 period when a number of long coral records are available. Current spatiotemporal gaps in data coverage and regions where significant potential for future proxy collection exists are discussed. We then highlight the need for new and extended records from key dynamical regions of the Southern Hemisphere. Although large-scale climate field reconstructions for the SH are in their infancy, we report that excellent progress in the development of regional proxies now makes plausible estimates of continental- to hemispheric-scale climate variations possible.

A Thalamic-Fronto-Parietal Structural Covariance Network Emerging in the Course of Recovery from Hand Paresis after Ischemic Stroke.

AIM To describe structural covariance networks of gray matter volume (GMV) change in 28 patients with first-ever stroke to the primary sensorimotor cortices, and to investigate their relationship to hand function recovery and local GMV change. METHODS Tensor-based morphometry maps derived from high-resolution structural images were subject to principal component analyses to identify the networks. We calculated correlations between network expression and local GMV change, sensorimotor hand function and lesion volume. To verify which of the structural covariance networks of GMV change have a significant relationship to hand function, we performed an additional multivariate regression approach. RESULTS Expression of the second network, explaining 9.1% of variance, correlated with GMV increase in the medio-dorsal (md) thalamus and hand motor skill. Patients with positive expression coefficients were distinguished by significantly higher GMV increase of this structure during stroke recovery. Significant nodes of this network were located in md thalamus, dorsolateral prefrontal cortex, and higher order sensorimotor cortices. Parameter of hand function had a unique relationship to the network and depended on an interaction between network expression and lesion volume. Inversely, network expression is limited in patients with large lesion volumes. CONCLUSION Chronic phase of sensorimotor cortical stroke has been characterized by a large scale co-varying structural network in the ipsilesional hemisphere associated specifically with sensorimotor hand skill. Its expression is related to GMV increase of md thalamus, one constituent of the network, and correlated with the cortico-striato-thalamic loop involved in control of motor execution and higher order sensorimotor cortices. A close relation between expression of this network with degree of recovery might indicate reduced compensatory resources in the impaired subgroup.

Conflict and cognitive control during sentence comprehension: recruitment of a frontal network during the processing of Spanish object-first sentences.

During sentence processing there is a preference to treat the first noun phrase found as the subject and agent, unless marked the other way. This preference would lead to a conflict in thematic role assignment when the syntactic structure conforms to a non-canonical object-before-subject pattern. Left perisylvian and fronto-parietal brain networks have been found to be engaged by increased computational demands during sentence comprehension, while event-reated brain potentials have been used to study the on-line manifestation of these demands. However, evidence regarding the spatiotemporal organization of brain networks in this domain is scarce. In the current study we used Magnetoencephalography to track spatio-temporally brain activity while Spanish speakers were reading subject- and object-first cleft sentences. Both kinds of sentences remained ambiguous between a subject-first or an object-first interpretation up to the appearance of the second argument. Results show the time-modulation of a frontal network at the disambiguation point of object-first sentences. Moreover, the time windows where these effects took place have been previously related to thematic role integration (300–500 ms) and to sentence reanalysis and resolution of conflicts during processing (beyond 500 ms post-stimulus). These results point to frontal cognitive control as a putative key mechanism which may operate when a revision of the sentence structure and meaning is necessary

Multi-Resolution Texture Coding for Multi-Resolution 3D Meshes

We present an innovative system to encode and transmit textured multi-resolution 3D meshes in a progressive way, with no need to send several texture images, one for each mesh LOD (Level Of Detail). All texture LODs are created from the finest one (associated to the finest mesh), but can be re- constructed progressively from the coarsest thanks to refinement images calculated in the encoding process, and transmitted only if needed. This allows us to adjust the LOD/quality of both 3D mesh and texture according to the rendering power of the device that will display them, and to the network capacity. Additionally, we achieve big savings in data transmission by avoiding altogether texture coordinates, which are generated automatically thanks to an unwrapping system agreed upon by both encoder and decoder.

Self-organizing cultured neural networks: Image analysis techniques for longitudinal tracking and modeling of the underlying network structure

Esta tesis estudia la evolución estructural de conjuntos de neuronas como la capacidad de auto-organización desde conjuntos de neuronas separadas hasta que forman una red (clusterizada) compleja. Esta tesis contribuye con el diseño e implementación de un algoritmo no supervisado de segmentación basado en grafos con un coste computacional muy bajo. Este algoritmo proporciona de forma automática la estructura completa de la red a partir de imágenes de cultivos neuronales tomadas con microscopios de fase con una resolución muy alta. La estructura de la red es representada mediante un objeto matemático (matriz) cuyos nodos representan a las neuronas o grupos de neuronas y los enlaces son las conexiones reconstruidas entre ellos. Este algoritmo extrae también otras medidas morfológicas importantes que caracterizan a las neuronas y a las neuritas. A diferencia de otros algoritmos hasta el momento, que necesitan de fluorescencia y técnicas inmunocitoquímicas, el algoritmo propuesto permite el estudio longitudinal de forma no invasiva posibilitando el estudio durante la formación de un cultivo. Además, esta tesis, estudia de forma sistemática un grupo de variables topológicas que garantizan la posibilidad de cuantificar e investigar la progresión de las características principales durante el proceso de auto-organización del cultivo. Nuestros resultados muestran la existencia de un estado concreto correspondiente a redes con configuracin small-world y la emergencia de propiedades a micro- y meso-escala de la estructura de la red. Finalmente, identificamos los procesos físicos principales que guían las transformaciones morfológicas de los cultivos y proponemos un modelo de crecimiento de red que reproduce el comportamiento cuantitativamente de las observaciones experimentales. ABSTRACT The thesis analyzes the morphological evolution of assemblies of living neurons, as they self-organize from collections of separated cells into elaborated, clustered, networks. In particular, it contributes with the design and implementation of a graph-based unsupervised segmentation algorithm, having an associated very low computational cost. The processing automatically retrieves the whole network structure from large scale phase-contrast images taken at high resolution throughout the entire life of a cultured neuronal network. The network structure is represented by a mathematical object (a matrix) in which nodes are identified neurons or neurons clusters, and links are the reconstructed connections between them. The algorithm is also able to extract any other relevant morphological information characterizing neurons and neurites. More importantly, and at variance with other segmentation methods that require fluorescence imaging from immunocyto- chemistry techniques, our measures are non invasive and entitle us to carry out a fully longitudinal analysis during the maturation of a single culture. In turn, a systematic statistical analysis of a group of topological observables grants us the possibility of quantifying and tracking the progression of the main networks characteristics during the self-organization process of the culture. Our results point to the existence of a particular state corresponding to a small-world network configuration, in which several relevant graphs micro- and meso-scale properties emerge. Finally, we identify the main physical processes taking place during the cultures morphological transformations, and embed them into a simplified growth model that quantitatively reproduces the overall set of experimental observations.

Self-organizing cultured neural networks: Image analysis techniques for longitudinal tracking and modeling of the underlying network structure (versión actualizada)

Esta tesis estudia la evolución estructural de conjuntos de neuronas como la capacidad de auto-organización desde conjuntos de neuronas separadas hasta que forman una red (clusterizada) compleja. Esta tesis contribuye con el diseño e implementación de un algoritmo no supervisado de segmentación basado en grafos con un coste computacional muy bajo. Este algoritmo proporciona de forma automática la estructura completa de la red a partir de imágenes de cultivos neuronales tomadas con microscopios de fase con una resolución muy alta. La estructura de la red es representada mediante un objeto matemático (matriz) cuyos nodos representan a las neuronas o grupos de neuronas y los enlaces son las conexiones reconstruidas entre ellos. Este algoritmo extrae también otras medidas morfológicas importantes que caracterizan a las neuronas y a las neuritas. A diferencia de otros algoritmos hasta el momento, que necesitan de fluorescencia y técnicas inmunocitoquímicas, el algoritmo propuesto permite el estudio longitudinal de forma no invasiva posibilitando el estudio durante la formación de un cultivo. Además, esta tesis, estudia de forma sistemática un grupo de variables topológicas que garantizan la posibilidad de cuantificar e investigar la progresión de las características principales durante el proceso de auto-organización del cultivo. Nuestros resultados muestran la existencia de un estado concreto correspondiente a redes con configuracin small-world y la emergencia de propiedades a micro- y meso-escala de la estructura de la red. Finalmente, identificamos los procesos físicos principales que guían las transformaciones morfológicas de los cultivos y proponemos un modelo de crecimiento de red que reproduce el comportamiento cuantitativamente de las observaciones experimentales. ABSTRACT The thesis analyzes the morphological evolution of assemblies of living neurons, as they self-organize from collections of separated cells into elaborated, clustered, networks. In particular, it contributes with the design and implementation of a graph-based unsupervised segmentation algorithm, having an associated very low computational cost. The processing automatically retrieves the whole network structure from large scale phase-contrast images taken at high resolution throughout the entire life of a cultured neuronal network. The network structure is represented by a mathematical object (a matrix) in which nodes are identified neurons or neurons clusters, and links are the reconstructed connections between them. The algorithm is also able to extract any other relevant morphological information characterizing neurons and neurites. More importantly, and at variance with other segmentation methods that require fluorescence imaging from immunocyto- chemistry techniques, our measures are non invasive and entitle us to carry out a fully longitudinal analysis during the maturation of a single culture. In turn, a systematic statistical analysis of a group of topological observables grants us the possibility of quantifying and tracking the progression of the main networks characteristics during the self-organization process of the culture. Our results point to the existence of a particular state corresponding to a small-world network configuration, in which several relevant graphs micro- and meso-scale properties emerge. Finally, we identify the main physical processes taking place during the cultures morphological transformations, and embed them into a simplified growth model that quantitatively reproduces the overall set of experimental observations.

Integration of circadian and phototransduction pathways in the network controlling CAB gene transcription in Arabidopsis

The transcription of CAB genes, encoding the chlorophyll a/b-binding proteins, is rapidly induced in dark-grown Arabidopsis seedlings following a light pulse. The transient induction is followed by several cycles of a circadian rhythm. Seedlings transferred to continuous light are known to exhibit a robust circadian rhythm of CAB expression. The precise waveform of CAB expression in light–dark cycles, however, reflects a regulatory network that integrates information from photoreceptors, from the circadian clock and possibly from a developmental program. We have used the luciferase reporter system to investigate CAB expression with high time resolution. We demonstrate that CAB expression in light-grown plants exhibits a transient induction following light onset, similar to the response in dark-grown seedlings. The circadian rhythm modulates the magnitude and the kinetics of the response to light, such that the CAB promoter is not light responsive during the subjective night. A signaling pathway from the circadian oscillator must therefore antagonize the phototransduction pathways controlling the CAB promoter. We have further demonstrated that the phase of maximal CAB expression is delayed in light–dark cycles with long photoperiods, due to the entrainment of the circadian oscillator. Under short photoperiods, this pattern of entrainment ensures that dawn coincides with a phase of high light responsiveness, whereas under long photoperiods, the light response at dawn is reduced.

Zinc- and iron-rubredoxins from Clostridium pasteurianum at atomic resolution: a high-precision model of a ZnS4 coordination unit in a protein.

The Zn(Scys)4 unit is present in numerous proteins, where it assumes structural, regulatory, or catalytic roles. The same coordination is found naturally around iron in rubredoxins, several structures of which have been refined at resolutions of, or near to, 1 A. The fold of the small protein rubredoxin around its metal ion is an excellent model for many zinc finger proteins. Zn-substituted rubredoxin and its Fe-containing counterpart were both obtained as the products of the expression in Escherichia coli of the rubredoxin-encoding gene from Clostridium pasteurianum. The structures of both proteins have been refined with an anisotropic model at atomic resolution (1.1 A, R = 8.3% for Fe-rubredoxin, and 1.2 A, R = 9.6% for Zn-rubredoxin) and are very similar. The most significant differences are increased lengths of the M-S bonds in Zn-rubredoxin (average length, 2.345 A) as compared with Fe-rubredoxin (average length, 2.262 A). An increase of the CA-CB-SG-M dihedral angles involving Cys-6 and Cys-39, the first cysteines of each of the Cys-Xaa-Xaa-Cys metal binding motifs, has been observed. Another consequence of the replacement of iron by zinc is that the region around residues 36-46 undergoes larger displacements than the remainder of the polypeptide chain. Despite these changes, the main features of the FeS4 site, namely a local 2-fold symmetry and the characteristic network of N-H...S hydrogen bonds, are conserved in the ZnS4 site. The Zn-substituted rubredoxin provides the first precise structure of a Zn(Scys)4 unit in a protein. The nearly identical fold of rubredoxin around iron or zinc suggests that at least in some of the sites where the metal has mainly a structural role-e.g., zinc fingers-the choice of the relevant metal may be directed by its cellular availability and mobilization processes rather than by its chemical nature.

European Bank Resolution: Making it work! Interim report of the CEPS Task Force on Implementing Financial Sector Resolution. CEPS Task Force Report, January 2016

From the start of 2016, new rules for bank resolution are in place – as spelled out in the Bank Recovery and Resolution Directive (BRRD) – across the EU, and a new authority (the Single Resolution Board, or SRB) is fully operational for resolving all banks in the eurozone. The implementation issues of the new regime are enormous. Banks need to develop recovery plans, and authorities need to create resolution plans as well as set the minimum required amount of own funds and eligible liabilities (MREL) for each bank. But given the diversity in bank structures and instruments at EU and global level, this will be a formidable challenge, above all with respect to internationally active banks. In order to explore ways in which the authorities and banks can meet this challenge, CEPS formed a Task Force composed of senior experts on banking sector reform and chaired by Thomas Huertas, Partner and Chair, EY Global Regulatory Network. This report contains its policy recommendations.

Methods for conflict resolution in policy-based management systems

While developments in distributed object computing environments, such as the Common Object Request Broker Architecture (CORBA) [17] and the Telecommunication Intelligent Network Architecture (TINA) [16], have enabled interoperability between domains in large open distributed systems, managing the resources within such systems has become an increasingly complex task. This challenge has been considered for several years within the distributed systems management research community and policy-based management has recently emerged as a promising solution. Large evolving enterprises present a significant challenge for policy-based management partly due to the requirement to support both mutual transparency and individual autonomy between domains [2], but also because the fluidity and complexity of interactions occurring within such environments requires an ability to cope with the coexistence of multiple, potentially inconsistent policies. This paper discusses the need of providing both dynamic (run-time) and static (compile-time) conflict detection and resolution for policies in such systems and builds on our earlier conflict detection work [7, 8] to introduce the methods for conflict resolution in large open distributed systems.