Assessing organo-clay dispersion in polymer layered silicate nanocomposites: A SAXS approach

A SAXS method for the quantitative assessment of the morphology of polymer layered silicate nanocomposites is proposed. Fitting the SAXS patterns, the number of clay layers, the periodicity of the layers in the tactoids, the thickness of the regions interposed between the clay platelets and their distributions can be measured. A good agreement with TEM data was obtained, avoiding the inconsistencies with microscopical observations often reported in the literature.     

Introduction

Concluding remarks With this brief exposition of the areas covered in this special double issue on Eurotra, we shall now conclude our introduction. We hope that the volume will achieve its goals, as outlined above, at least to some extent. Certainly, much more could be said about a wide range of topics which have been covered in the lifetime or the project so far. For instance, these article, mainly written by linguists, deliberately neglect the software implementation and environment aspects of the prototype Eurotra Translation System, as well as a number of peripheral tools and components of the system that are available to the user, such as lexical data bases, text-handling mechanisms and the like. The reader interested in aspects of this kind is referred to Raw et al. 1989 for a very brief introduction, and to the Eurotra software team at the Commission of the European Communities (DG XIII, Luxembourg) for more details. However, one goal that we do hope to come close to achieving is to give a fair overview of the Eurotra linguistic theory of translation and the mainstream and sideline formalisms expressing variant versions of it. If we have come anywhere near achieving that, our gratitude is due to the numerous Eurotra colleagues who have supported us in preparing this volume, and to the editor of this journal.     

Do WHO-ISH guidelines identify high risk mild hypertensive patients?

OBJECTIVE: To assess the ability of 1993 WHO-ISH recommendations to identify patients who need drug treatment. METHODS: 268 hypertensive patients with suspected mild hypertension were preselected for this study at their first visit at the referral center. 123 were included after a short in-hospital work-up when they fulfilled the 1993 WHO-ISH criteria for mild hypertension (90-105 mmHg diastolic BP and/or 140-180 mmHg systolic BP). Echocardiography was performed in all patients by the same investigator according to ASE convention. The combined 10-year risk of stroke and coronary heart disease was calculated with the Framingham equation. Patients were then followed up for six months by the same physician blinded to echographic results and risk calculations and applying the WHO-ISH guidelines (monthly BP measurement and subjective assessment of risk). Five patients were excluded, for reasons unrelated to the protocol. RESULTS: The decision of drug treatment was taken at the 1st, 2nd, 3rd, 4th, 5th, 6th monthly visit after work-up in 2, 6, 25, 7, 2 and 6 patients, respectively. Among these 118 patients, 48 patients (29 male, 19 female) were eventually treated and 70 (49 male, 30 female) remained untreated. BP s at preselection and on a day of work-up were similar in both groups. Patients in whom drug treatment was prescribed were older and had higher lef ventricular mass (LVM) than untreated patients, but only 2 of them (all in the treated group) had LVM values above usual thresholds (LVM > 125 g/m2, in men and women). Stroke and coronary risks were both higher in treated than in untreated patients (p < 0.05). The physician using the guidelines decided to treat only 19 of the 38 patients with a 10-year risk < 10% (true positive), whereas she decided to treat with drugs 12 patients among the 44 with a 10-year risk < 5%. CONCLUSION: The difference in LVM between untreated and treated patients support the validity of the WHO-ISH guidelines, but the measurement of LVM did not bring much information for managing the individual patient. Application of these guidelines did not satisfactorily identify high risk patients and could lead to over-treatment of low risk patients.     

Transporting Deformations of Face Emotions in the Shape Spaces: A Comparison of Different Approaches

Studying the changes of shape is a common concern in many scientific fields. We address here two problems: (1) quantifying the deformation between two given shapes and (2) transporting this deformation to morph a third shape. These operations can be done with or without point correspondence, depending on the availability of a surface matching algorithm, and on the type of mathematical procedure adopted. In computer vision, the re-targeting of emotions mapped on faces is a common application. We contrast here four different methods used for transporting the deformation toward a target once it was estimated upon the matching of two shapes. These methods come from very different fields such as computational anatomy, computer vision and biology. We used the large diffeomorphic deformation metric mapping and thin plate spline, in order to estimate deformations in a deformational trajectory of a human face experiencing different emotions. Then we use naive transport (NT), linear shift (LS), direct transport (DT) and fanning scheme (FS) to transport the estimated deformations toward four alien faces constituted by 240 homologous points and identifying a triangulation structure of 416 triangles. We used both local and global criteria for evaluating the performance of the 4 methods, e.g., the maintenance of the original deformation. We found DT, LS and FS very effective in recovering the original deformation while NT fails under several aspects in transporting the shape change. As the best method may differ depending on the application, we recommend carefully testing different methods in order to choose the best one for any specific application.

     

Interactive quadrangulation with Reeb atlases and connectivity textures

Creating high-quality quad meshes from triangulated surfaces is a highly nontrivial task that necessitates consideration of various application specific metrics of quality. In our work, we follow the premise that automatic reconstruction techniques may not generate outputs meeting all the subjective quality expectations of the user. Instead, we put the user at the center of the process by providing a flexible, interactive approach to quadrangulation design. By combining scalar field topology and combinatorial connectivity techniques, we present a new framework, following a coarse to fine design philosophy, which allows for explicit control of the subjective quality criteria on the output quad mesh, at interactive rates. Our quadrangulation framework uses the new notion of Reeb atlas editing, to define with a small amount of interactions a coarse quadrangulation of the model, capturing the main features of the shape, with user prescribed extraordinary vertices and alignment. Fine grain tuning is easily achieved with the notion of connectivity texturing, which allows for additional extraordinary vertices specification and explicit feature alignment, to capture the high-frequency geometries. Experiments demonstrate the interactivity and flexibility of our approach, as well as its ability to generate quad meshes of arbitrary resolution with high-quality statistics, while meeting the user’s own subjective requirements.     

The GAUGAA Motif Is Responsible for the Binding between circSMARCA5 and SRSF1 and Related Downstream Effects on Glioblastoma Multiforme Cell Migration and Angiogenic Potential

Circular RNAs (circRNAs) are a large class of RNAs with regulatory functions within cells. We recently showed that circSMARCA5 is a tumor suppressor in glioblastoma multiforme (GBM) and acts as a decoy for Serine and Arginine Rich Splicing Factor 1 (SRSF1) through six predicted binding sites (BSs). Here we characterized RNA motifs functionally involved in the interaction between circSMARCA5 and SRSF1. Three different circSMARCA5 molecules (Mut1, Mut2, Mut3), each mutated in two predicted SRSF1 BSs at once, were obtained through PCR-based replacement of wild-type (WT) BS sequences and cloned in three independent pcDNA3 vectors. Mut1 significantly decreased its capability to interact with SRSF1 as compared to WT, based on the RNA immunoprecipitation assay. In silico analysis through the “Find Individual Motif Occurrences” (FIMO) algorithm showed GAUGAA as an experimentally validated SRSF1 binding motif significantly overrepresented within both predicted SRSF1 BSs mutated in Mut1 (q-value = 0.0011). U87MG and CAS-1, transfected with Mut1, significantly increased their migration with respect to controls transfected with WT, as revealed by the cell exclusion zone assay. Immortalized human brain microvascular endothelial cells (IM-HBMEC) exposed to conditioned medium (CM) harvested from U87MG and CAS-1 transfected with Mut1 significantly sprouted more than those treated with CM harvested from U87MG and CAS-1 transfected with WT, as shown by the tube formation assay. qRT-PCR showed that the intracellular pro- to anti-angiogenic Vascular Endothelial Growth Factor A (VEGFA) mRNA isoform ratio and the amount of total VEGFA mRNA secreted in CM significantly increased in Mut1-transfected CAS-1 as compared to controls transfected with WT. Our data suggest that GAUGAA is the RNA motif responsible for the interaction between circSMARCA5 and SRSF1 as well as for the circSMARCA5-mediated control of GBM cell migration and angiogenic potential.     

Morphology, structure and properties of a poly(1-butene)/montmorillonite nanocomposite

A specifically formulated nanocomposite based on isotactic poly(1-butene) (PB) and montmorillonite was studied, by wide angle X-ray diffraction (WAXD), small angle X-ray scattering (SAXS), transmission electron microscopy (TEM) and polarized light optical microscopy, investigating the polymorphism of the polymer, and examining the interaction between PB and the silicate. Montmorillonite was found to disrupt the ordered morphology of the polymer, determining a dramatic increase in the rate of the II→I phase transition. Interaction between polymer and clay was studied by TEM and SAXS also under a quantitative point of view. A significant enhancement of physical-mechanical properties was observed, even though exfoliation did not occur, but just a slight intercalation and a reduction in the size of tactoids.     

Electrochemical characterization of 8-hydroxyquinoline-5-sulphonate/aluminium(III) aqueous solutions

8-Hydroxyquinoline-5-sulphonate/Al(III) aqueous solutions were studied both by potentiometric titrations and voltammetric measurements, in order to obtain the number, the stoichiometry and the stability constants of the complexes formed at equilibrium, and to evaluate the redox and (electro)kinetic properties of the free ligand and of the metal/ligand complexes. The complexes formed in 0.2 m (Na)Cl aqueous solution (stability log beta values ± standard deviation) are AlL⁺ (8.95 ± 0.05), AlL₂⁻ (17.43 ± 0.03) and AlL₃³⁻ (24.58 ± 0.05), where “L” denotes the free ligand in the completely deprotonated form (L²⁻, pK_a1 = 3.910 ± 0.008, pK_a2 = 8.319 ± 0.004). AlL₃³⁻ is the predominant Al(III) species in a very wide range of pH, metal and ligand concentrations and metal-to-ligand ratios. The free ligand shows an oxidation wave at 0.62 V versus SCE. The proposed oxidation mechanism includes a first reversible one-electron oxidation of the ligand, followed by a coupling reaction and by a second reversible one-electron oxidation, and finally by a decomposition reaction. The addition of Al(III) lowers the intensity of the oxidation wave due to the formation of the redox-inactive complex AlL₃³⁻. A residual low signal was attributed to the free ligand produced by the complex dissociation, AlL₃³⁻ = AlL₂⁻ + L²⁻. All the kinetic parameters involved in the ligand oxidation and in the complex disruption were calculated on the basis of the agreement between experimental and simulated linear sweep and cyclic voltammetries. Correctness of the mechanisms proposed was further confirmed “a posteriori” by the agreement between potentiometric and linear sweep voltammetric results. The low residual signal observed in the presence of fully formed complex was attributed to the free ligand produced by the complex dissociation, having a kinetic constant estimated 0.2 s⁻¹.     

On arginine-based polyurethane-blends specific to vascular prostheses

Polymer blends based on Tecoflex™ and an experimental aliphatic polyurethane (HMDI-PCL-arginine stands for 4,4 (metylene-biscyclohexyl) isocyanate - poly (ε caprolactone) diol, SPUUR stands for segmented poly(urea)urethanes using amino acid of L-Arginine as chain extender) were obtained by solvent casting, and further studied by fourier transform infrared (FTIR) and Raman spectroscopy, differential scanning calorimetry (DSC), thermogravimetric analysis, and X-ray diffraction (XRD). Their biological performances were assessed in terms of hemocompatibility and Human umbilical vein endothelial cell (HUVEC) cytotoxicity. Tensile properties of dumbbell specimens were compared to longitudinal and circumferential tensile properties of tubular vascular graft. FTIR showed that as the SPUUR content increased in the blend, absorptions at 2860 cm⁻¹ increased, carbonyl absorptions at 1724 cm⁻¹ broaden and the small peak at 2796 cm⁻¹, typical of Tecoflex™ disappeared. Raman spectroscopy showed that the low intensity carbonyl absorption at 1724 cm⁻¹ also increased with SPUUR content. DSC allowed detection of PCL soft segment melting (T_m = 50°C) in agreement with X-ray reflections at 21.3° and 23.6°, assigned to SPUUR. However, no improvements in thermal stability were detected by TGA by blending. The addition of SPUUR to Tecoflex™ improved hemocompatibility and HUVEC cytotoxicity. The vascular grafts performance showed that 40% SPUUR blends exhibited the highest force in the longitudinal test whereas 50% SPUUR blends showed the highest circumferential force. Pressure burst strength was higher than 1000 mmHg for all blends. Overall, these blends can be used for high caliber vascular grafts.     

Information diffusion in distributed OSN: The impact of trusted relationships

Distributed Online Social Networks (DOSN) are a valid alternative to OSN based on peer-to-peer communications. Without centralised data management, DOSN must provide the users with higher level of control over their personal information and privacy. Thus, users may wish to restrict their personal network to a limited set of peers, depending on the level of trust with them. This means that the effective social network (used for information exchange) may be a subset of the complete social network, and may present different structural patterns, which could limit information diffusion. In this paper, we estimate the capability of DOSN to diffuse content based on trust between social peers. To have a realistic representation of a OSN friendship graph, we consider a large-scale Facebook network, from which we estimate the trust level between friends. Then, we consider only social links above a certain threshold of trust, and we analyse the potential capability of the resulting graph to spread information through several structural indices. We test four possible thresholds, coinciding with the definition of personal social circles derived from sociology and anthropology. The results show that limiting the network to “active social contacts” leads to a graph with high network connectivity, where the nodes are still well-connected to each other, thus information can potentially cover a large number of nodes with respect to the original graph. On the other hand, the coverage drops for more restrictive assumptions. Nevertheless the re-insertion of a single excluded friend for each user is sufficient to obtain good coverage (i.e., always higher than 40 %) even in the most restricted graphs. We also analyse the potential capability of the network to spread information (i.e., network spreadability), studying the properties of the social paths between any pairs of users in the graph, which represent the effective channels traversed by information. The value of contact frequency between pairs of users determines a decay of trust along the path (the higher the contact frequency the lower the decay), and a consequent decay in the level of trustworthiness of information traversing the path. We show that selecting the link to re-insert in the network with probability proportional to its level of trust is the best re-insertion strategy, as it leads to the best connectivity/spreadability combination.