DFT STUDIES ON THE MECHANISM OF RING-OPENING POLYMERIZATION OF LACTIDE WITH ADENINE

The use of organic molecules as catalysts for the ring-opening polymerization (ROP) of cyclic esters has gained much interest last years.[1] The use of a molecule of biological interest, able to initiate ROP of cyclic esters without any cocatalyst is even more interesting, as the resulting material will not contain any catalytic residue. Nucleobase-polymer conjugates development is thus an emerging area envisaging biomedical applications.[2] However, they are usually synthesized by tedious multistep procedures. Recently, adenine was used as organoinitiator for the ROP of L-lactide.[3] Reaction conditions involving short reaction times and relatively low temperatures enable the access to adenine-polylactide(Adn-PLA)conjugates in a simple one-step procedure, without additional catalyst and in the absence of solvent. In this study, computational investigations with density functional theory (DFT) were performed in order to clarify the reaction mechanism leading to the desired Adn-PLA. The results show that a hydrogen bond catalytic mechanism, involving a nucleophilic attack of the activated amine group of adenine onto the carbonyl group of lactide, seem to be plausible.

Clustering of Territorial Areas: A Multicriteria Districting problem

The success of regional development policies depends on the homogeneity of the territorial units. This paper aims to propose a framework for obtaining homogenous territorial clusters based on a Pareto frontier considering multiple criteria related to territories’ endogenous resources, economic profile and socio-cultural features. This framework is developed in two phases. First, the criteria correlated with development at the territorial unit level are determined through statistical and econometric methods. Then, a multi-criteria approach is developed to allocate each territorial unit (parishes) to a territorial agglomerate, according to the Pareto frontier established.

The Selection Process of Applications to the Portuguese Innovation Incentive System: Who Gets Financial Support?

Public policies to support entrepreneurship and innovation play a vital role when firms have difficulties in accessing external finance. However, some authors have found evidence of long-term inefficiency in subsidized firms (Bernini and Pelligrini, 2011; Cerqua and Pelligrini, 2014) and ineffectiveness of public funds (Jorge and Suárez, 2011). The aim of the paper is to assess the effectiveness in the selection process of applications to public financial support for stimulating innovation. Using a binary choice model, we investigate which factors influence the probability of obtaining public support for an innovative investment. The explanatory variables are connected to firm profile, the characteristics of the project and the macroeconomic environment. The analysis is based on the case study of the Portuguese Innovation.Incentive System (PIIS) and on the applications managed by the Alentejo Regional Operational Program in the period 2007 – 2013. The results show that the selection process is more focused on the expected impact of the project than on the firm’s past performance. Factors that influence the credit risk and the decision to grant a bank loan do not seem to influence the government evaluator regarding the funding of some projects. Past activities in R&D do not significantly affect the probability of having an application approved under the PIIS, whereas an increase in the number of patents and the number of skilled jobs are both relevant factors. Nevertheless, some evidence of firms’ short-term inefficiency was found, in that receiving public financial support is linked to a smaller increase in productivity compared to non-approved firm applications. At the macroeconomic level, periods with a higher cost of capital in financial markets are linked to a greater probability of getting an application for public support approved, which could be associated with the effectiveness of public support in correcting market failings.

Hierarchical spatial segregation of two Mediterranean vole species: the role of patch‑network structure and matrix composition

According to ecological theory, the coexistence of competitors in patchy environments may be facilitated by hierarchical spatial segregation along axes of environmental variation, but empirical evidence is limited. Cabrera and water voles show a metapopulation-like structure in Mediterranean farmland, where they are known to segregate along space, habitat, and time axes within habitat patches. Here, we assess whether segregation also occurs among and within landscapes, and how this is influenced by patch-network and matrix composition. We surveyed 75 landscapes, each covering 78 ha, where we mapped all habitat patches potentially suitable for Cabrera and water voles, and the area effectively occupied by each species (extent of occupancy). The relatively large water vole tended to be the sole occupant of landscapes with high habitat amount but relatively low patch density (i.e., with a few large patches), and with a predominantly agricultural matrix, whereas landscapes with high patch density (i.e.,many small patches) and low agricultural cover, tended to be occupied exclusively by the small Cabrera vole. The two species tended to co-occur in landscapes with intermediate patch-network and matrix characteristics, though their extents of occurrence were negatively correlated after controlling for environmental effects. In combination with our previous studies on the Cabrera-water vole system, these findings illustrated empirically the occurrence of hierarchical spatial segregation, ranging from withinpatches to among-landscapes. Overall, our study suggests that recognizing the hierarchical nature of spatial segregation patterns and their major environmental drivers should enhance our understanding of species coexistence in patchy environments.

Development and characterization of innovative graphene-based composites

Over the last decade, graphene and related materials (GRM) have drawn significant interest and resources for their development into the next generation of composite materials. This is because these nanoparticles have the ability to operate as reinforcing additives capable of imparting considerable mechanical property increases while also embedding multi-functional advantages on the host matrix. Because graphene and 2D materials are still in their early stages, the relative maturity of different types of composite systems varies. As a result, certain nanocomposite systems are currently commercially accessible, while others are not yet sufficiently developed to enter the market. A substantial emphasis has been placed on developing thermoplastic and thermosetting materials that combine a variety of mechanical and functional qualities. These include higher strength and stiffness, increased thermal and electrical conductivity, improved barrier properties, fire retardancy, and others, with the ultimate goal of providing multifunctionality to already employed composites. The work presented in this thesis investigates the use and benefits that GRM could bring to composites for a variety of applications, with the goal of realizing multifunctional components with improved properties that leads to lightweight and, as a result, energy and cost savings and pollution reduction in the environment. In particular, we worked on the following topics: • Benchmarking of commercial GRM-based master batches; • GRM-coatings for water uptake reduction; • GRM as thermo-electrical anti-icing /de-icing system; • GRM for Out of Oven curing of composites.

Exploiting the clustering of cosmic voids as a novel cosmological probe

The investigations of the large-scale structure of our Universe provide us with extremely powerful tools to shed light on some of the open issues of the currently accepted Standard Cosmological Model. Until recently, constraining the cosmological parameters from cosmic voids was almost infeasible, because the amount of data in void catalogues was not enough to ensure statistically relevant samples. The increasingly wide and deep fields in present and upcoming surveys have made the cosmic voids become promising probes, despite the fact that we are not yet provided with a unique and generally accepted definition for them. In this Thesis we address the two-point statistics of cosmic voids, in the very first attempt to model its features with cosmological purposes. To this end, we implement an improved version of the void power spectrum presented by Chan et al. (2014). We have been able to build up an exceptionally robust method to tackle with the void clustering statistics, by proposing a functional form that is entirely based on first principles. We extract our data from a suite of high-resolution N-body simulations both in the LCDM and alternative modified gravity scenarios. To accurately compare the data to the theory, we calibrate the model by accounting for a free parameter in the void radius that enters the theory of void exclusion. We then constrain the cosmological parameters by means of a Bayesian analysis. As far as the modified gravity effects are limited, our model is a reliable method to constrain the main LCDM parameters. By contrast, it cannot be used to model the void clustering in the presence of stronger modification of gravity. In future works, we will further develop our analysis on the void clustering statistics, by testing our model on large and high-resolution simulations and on real data, also addressing the void clustering in the halo distribution. Finally, we also plan to combine these constraints with those of other cosmological probes.

Performance Analysis of 5G based Positioning in Railway Applications

Rail transportation has significant importance in the future world. This importance is tightly bounded to accessible, sustainable, efficient and safe railway systems. Precise positioning in railway applications is essential for increasing railway traffic, train-track control, collision avoidance, train management and autonomous train driving. Hence, precise train positioning is a safety-critical application. Nowadays, positioning in railway applications highly depends on a cellular-based system called GSM-R, a railway-specific version of Global System for Mobile Communications (GSM). However, GSM-R is a relatively outdated technology and does not provide enough capacity and precision demanded by future railway networks. One option for positioning is mounting Global Navigation Satellite System (GNSS) receivers on trains as a low-cost solution. Nevertheless, GNSS can not provide continuous service due to signal interruption by harsh environments, tunnels etc. Another option is exploiting cellular-based positioning methods. The most recent cellular technology, 5G, provides high network capacity, low latency, high accuracy and high availability suitable for train positioning. In this thesis, an approach to 5G-based positioning for railway systems is discussed and simulated. Observed Time Difference of Arrival (OTDOA) method and 5G Positioning Reference Signal (PRS) are used. Simulations run using MATLAB, based on existing code developed for 5G positioning by extending it for Non Line of Sight (NLOS) link detection and base station exclusion algorithms. Performance analysis for different configurations is completed. Results show that efficient NLOS detection improves positioning accuracy and implementing a base station exclusion algorithm helps for further increase.

Reduced Lrp6 Expression And Increase In The Interaction Of Gsk3β With P53 Contribute To Podocyte Apoptosis In Diabetes Mellitus And Are Prevented By Green Tea.

In diabetes mellitus (DM), podocyte apoptosis leads to albuminuria and nephropathy progression. Low-density lipoprotein receptor-related protein 6 (LRP6) is WNT pathway receptor that is involved in podocyte death, adhesion and motility. Glycogen synthase kinase 3 (GSK3) interaction with p53 (GSK3-p53) promotes apoptosis in carcinoma cells. It is unknown if GSK3-p53 contributes to podocyte apoptosis in DM. In experimental DM, green tea (GT) reduces albuminuria by an unknown mechanism. In the present study, we assessed the role of the GSK3β-p53 in podocyte apoptosis and the effects of GT on these abnormalities. In diabetic spontaneously hypertensive rats (SHRs), GT prevents podocyte's p-LRP6 expression reduction, increased GSK3β-p53 and high p53 levels. In diabetic SHR rats, GT reduces podocyte apoptosis, foot process effacement and albuminuria. In immortalized mouse podocytes (iMPs), high glucose (HG), silencing RNA (siRNA) or blocking LRP6 (DKK-1) reduced p-LRP6 expression, leading to high GSK3β-p53, p53 expression, apoptosis and increased albumin influx. GSK3β blockade by BIO reduced GSK3β-p53 and podocyte apoptosis. In iMPs under HG, GT reduced apoptosis and the albumin influx by blocking GSK3β-p53 following the rise in p-LRP6 expression. These effects of GT were prevented by LRP6 siRNA or DKK-1. In conclusion, in DM, WNT inhibition, via LRP6, increases GSK3β-p53 and podocyte apoptosis. Maneuvers that inactivate GSK3β-p53, such as GT, may be renoprotective in DM.

Evaluation of post-surgical healing in rats using a topical preparation based on extract of Musa sapientum L., Musaceae, epicarp

Considering that oral preparations made with peel green bananas (e.g. flour and extracts) demonstrated healing effects on mucous membranes and skin, this study evaluated the healing and the antimicrobial property of a topical preparation based on extract of Musa sapientum L., Musaceae, (apple banana) in surgically induced wounds in the skin of male Wistar rats, 100 g. The extract was obtained by decoction, the presence of tannins was detected by phytochemical screening and 10% of the extract was incorporated into the carbopol gel (CMS gel). The processes of healing and bacterial isolation were evaluated in the following experimental groups: control (no treatment), treatment with placebo or with the CMS gel. The healing of surgical wounds treated with the CMS gel was faster when compared with the control and placebo groups and the treatment with CMS gel also inhibited the growth of pyogenic bacteria and enterobacteria in the wounds. The results indicate that the extract of Musa sapientum epicarp has healing and antimicrobial properties (in vivo), probably, due to tannins.

Phase transitions in biodegradable films based on blends of gelatin and poly (vinyl alcohol)

The aim of this work was to study the effect of the hydrolysis degree (HD) and the concentration (C PVA) of two types of poly (vinyl alcohol) (PVA) and the effect of the type and the concentration of plasticizers on the phase properties of biodegradable films based on blends of gelatin and PVA, using a response-surface methodology. The films were made by casting and the studied properties were their glass (Tg) and melting (Tm) transition temperatures, which were determined by diferential scanning calorimetry (DSC). For the data obtained on the first scan, the fitting of the linear model was statistically significant and predictive only for the second melting temperature. In this case, the most important effect on the second Tm of the first scan was due to the HD of the PVA. In relation to the second scan, the linear model could be fit to Tg data with only two statistically significant parameters. Both the PVA and plasticizer concentrations had an important effect on Tg. Concerning the second Tm of the second scan, the linear model was fit to data with two statistically significant parameters, namely the HD and the plasticizer concentration. But, the most important effect was provoked by the HD of the PVA.

A biosensor based on immobilization of lactate oxidase in a PB-CTAB film for FIA determination of lactate in beer samples

An amperometric lactate biosensor with lactate oxidase immobilized into a Prussian Blue (PB) modified electrode was fabricated. The advantage of using cetyltrimethylammonium bromide (CTAB) in the electrodeposition step of PB films onto glassy carbon surfaces was confirmed taking into account both the stability and sensitivity of the measurements. The biosensor was used in the development of a FIA amperometric method for the determination of lactate. Under optimal operating conditions (pH = 6.9, E = -0.1 V), the linear response of the method was extended up to 0.28 µmol L-1 lactate with a limit of detection of 0.84 mmol L-1. The repeatability of the method for injections of a 0.28 mmol L-1 lactate solution was 2.2 % (n = 18). The usefulness of the method was demonstrated by determining lactate in beer samples and the results were in good agreement with those obtained by using a reference spectrophotometric enzyme method.

Population-based multicentric survey of hepatitis B infection and risk factor differences among three regions in Brazil

This multicentric population-based study in Brazil is the first national effort to estimate the prevalence of hepatitis B (HBV) and risk factors in the capital cities of the Northeast, Central-West, and Federal Districts (2004-2005). Random multistage cluster sampling was used to select persons 13-69 years of age. Markers for HBV were tested by enzyme-linked immunosorbent assay. The HBV genotypes were determined by sequencing hepatitis B surface antigen (HBsAg). Multivariate analyses and simple catalytic model were performed. Overall, 7,881 persons were included; < 70 per cent were not vaccinated. Positivity for HBsAg was less than 1 per cent among non-vaccinated persons and genotypes A, D, and F co-circulated. The incidence of infection increased with age with similar force of infection in all regions. Males and persons having initiated sexual activity were associated with HBV infection in the two settings; healthcare jobs and prior hospitalization were risk factors in the Federal District. Our survey classified these regions as areas with HBV endemicity and highlighted the risk factors differences among the settings

Density functional theory study of Fe(3)Ga

First-principles scalar relativistic calculations in supercells of 16 atoms are used to represent disordered B2 ordering of Fe(3)Ga in order to observe the effect of Ga-Ga pairs on the electronic structure of this alloy. From a comparison with pure bcc Fe it is observed that the energy position and occupation of e(g) and t(2g) states are largely affected by the Ga-Ga pairs and strengthened intraplane interactions takes place. The results show that a larger hybridization of the conduction band is in the source of the magnetostriction enhancement experimentally observed in Galfenol. (C) 2011 American Institute of Physics. [doi:10.1063/1.3525609]

Prevalence, Incidence Density, and Genotype Distribution of GB Virus C Infection in a Cohort of Recently HIV-1-Infected Subjects in Sao Paulo, Brazil

Background: The results of previous studies elsewhere have indicated that GB virus C (GBV-C) infection is frequent in patients infected with the human immunodeficiency virus type 1 (HIV-1) due to similar transmission routes of both viruses. The aim of this study was to determine the prevalence, incidence density and genotypic characteristics of GBV-C in this population. Methodology/Principal Findings: The study population included 233 patients from a cohort primarily comprised of homosexual men recently infected with HIV-1 in Sao Paulo, Brazil. The presence of GBV-C RNA was determined in plasma samples by reverse transcriptase-nested polymerase chain reaction and quantified by real-time PCR. GBV-C genotypes were determined by direct sequencing. HIV viral load, CD4+ T lymphocyte and CD8+ T lymphocyte count were also tested in all patients. The overall prevalence of GBV-C infection was 0.23 (95% CI: 0.18 to 0.29) in the study group. There was no significant difference between patients with and without GBV-C infection and Glycoprotein E2 antibody presence regarding age, sex, HIV-1 viral load, CD4+ and CD8+ T cell counts and treatment with antiretroviral drugs. An inverse correlation was observed between GBV-C and HIV-1 loads at enrollment and after one year. Also, a positive but not significant correlation was observed between GBV-C load and CD4+ T lymphocyte. Phylogenetic analysis of the GBV-C isolates revealed the presence of genotype 1 and genotype 2, these sub classified into subtype 2a and 2b. Conclusion/Significance: GBV-C infection is common in recently HIV -1 infected patients in Sao Paulo, Brazil and the predominant genotype is 2b. This study provides the first report of the GBV-C prevalence at the time of diagnosis of HIV-1 and the incidence density of GBV-C infection in one year.

Density functional theory investigation of 3d, 4d, and 5d 13-atom metal clusters

The knowledge of the atomic structure of clusters composed by few atoms is a basic prerequisite to obtain insights into the mechanisms that determine their chemical and physical properties as a function of diameter, shape, surface termination, as well as to understand the mechanism of bulk formation. Due to the wide use of metal systems in our modern life, the accurate determination of the properties of 3d, 4d, and 5d metal clusters poses a huge problem for nanoscience. In this work, we report a density functional theory study of the atomic structure, binding energies, effective coordination numbers, average bond lengths, and magnetic properties of the 3d, 4d, and 5d metal (30 elements) clusters containing 13 atoms, M(13). First, a set of lowest-energy local minimum structures (as supported by vibrational analysis) were obtained by combining high-temperature first- principles molecular-dynamics simulation, structure crossover, and the selection of five well-known M(13) structures. Several new lower energy configurations were identified, e. g., Pd(13), W(13), Pt(13), etc., and previous known structures were confirmed by our calculations. Furthermore, the following trends were identified: (i) compact icosahedral-like forms at the beginning of each metal series, more opened structures such as hexagonal bilayerlike and double simple-cubic layers at the middle of each metal series, and structures with an increasing effective coordination number occur for large d states occupation. (ii) For Au(13), we found that spin-orbit coupling favors the three-dimensional (3D) structures, i.e., a 3D structure is about 0.10 eV lower in energy than the lowest energy known two-dimensional configuration. (iii) The magnetic exchange interactions play an important role for particular systems such as Fe, Cr, and Mn. (iv) The analysis of the binding energy and average bond lengths show a paraboliclike shape as a function of the occupation of the d states and hence, most of the properties can be explained by the chemistry picture of occupation of the bonding and antibonding states.