Laccase-assisted approach to graft multifunctional materials of interest: keratin-EC based novel composites and their characterisation

This study focuses on the evaluation of raw keratin as a potential material to develop composites with novel characteristics. Herein, we report a mild and eco-friendly fabrication of in-house extracted feather keratin-based novel enzyme assisted composites consisting of ethyl cellulose (EC) as a backbone material. A range of composites between keratin and EC using different keratin: EC ratios were prepared and characterised. Comparing keratin to the composites, the FT-IR peak at 1,630 cm-1 shifted to a lower wavenumber of 1,610 cm-1 in keratin-EC which typically indicates the involvement of β-sheet structures of the keratin during the graft formation process. SEM analysis revealed that the uniform dispersion of the keratin increases the area of keratin-EC contact which further contributes to the efficient functionality of the resulting composites. In comparison to the pristine keratin and EC, a clear shift in the XRD peaks was also observed at the specific region of 2-Theta values of keratin-g-EC. The thermo- mechanical properties of the composites reached their highest levels in comparison to the keratin which was too fragile to be measured for its mechanical properties. Considerable improvement in the water contact angle and surface tension properties was also recorded.

Enzymatic grafting: A novel approach to develop multifunctional materials of interest

Today more than 99% of plastics are petroleum-based because of the availability and cost of the raw material. The durability of disposed plastics contributes to the environmental problems as waste and their persistence in the environment causes deleterious effects on the ecosystem. Environmental pollution awareness and the demand for green technology have drawn considerable attention of both academia and industry into biodegradable polymers. In this regard green chemistry technology has the potential to provide solution to this issue. Enzymatic grafting has recently been the focus of green chemistry technologies due to the growing environmental concerns, legal restrictions, and increasing availability of scientific knowledge. Over the last several years, research covering various applications of robust enzymes like laccases and lipases has been increased rapidly, particularly in the field of polymer science, to graft multi-functional materials of interest. In principle, enzyme-assisted grafting may modify/impart a variety of functionalities to the grafted composites which individual materials fail to demonstrate on their own. The modified polymers through grafting have a bright future and their development is practically boundless. In the present study series of graft composites with poly(3-hydroxybutyrate) (P(3HB) as side chain and cellulose as a backbone polymer were successfully synthesised by introducing enzymatic grafting technique where laccase and lipase were used as model catalysts [1-3]. Subsequently, the resulting composites were removed from the casting surface under ambient environment and characterised by Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), and X-ray diffraction (XRD) in detail. Moreover, the thermo-mechanical behaviours of the grafted composites were investigated by differential scanning calorimetry (DSC) and dynamic mechanical analyser (DMA) measurements, respectively. In addition, hydrophobic and hydrophilic characteristics of the grafted polymers were studied through drop contour analysis using water contact angle (WCA). In comparison to the individual counterparts improvement was observed in the thermo- mechanical properties of the composites to varied extent. The tensile strength, elongation at break, and Young’s modulus values of the composites reached their highest levels in comparison to the films prepared with pure P(3HB) only which was too fragile to measure any of the above said characteristics. Interestingly, untreated P(3HB) was hydrophobic in nature and after lipase treatment P(3HB) and P(3HB)-EC-based graft composite attained higher level of hydrophilicity. This is a desired characteristic that enhances the biocompatibility of the materials for proper cell adhesion and proliferation therefore suggesting potential candidates for tissue engineering/bio-medical type applications [3]. The present research will be a first step in the biopolymer modification. To date no report has been found in literature explaining the laccase/lipase assisted grafting of P(3HB) [1-3]. The newly grafted composites exhibit unique functionalities with wider range of potential applications in bio-plastics, pharmaceutical, and cosmetics industries, tissue engineering, and biosensors. [1] H.M.N. Iqbal, G. Kyazze, T. Tron and T. Keshavarz, Cellulose 21, 3613-3621 (2014). [2] H.M.N. Iqbal, G. Kyazze, T. Tron and T. Keshavarz, Carbohydrate Polymers 113, 131-137 (2014). [3] H.M.N. Iqbal, G. Kyazze, T. Tron and T. Keshavarz, Polymer Chemistry In-Press, DOI: 10.1039/C4PY0 0857J (2014).

Reliability of nasal auscultation and their relation to middle ear condition – a clinical interest to pediatrics respiratory physiotherapy

Background: Acute respiratory infections are usual in children under three years old occurring in upper respiratory tract, having an impact on child and caregiver’s quality of life predisposing to otitis media or bronchiolitis. There are few valid and reliable measures to determine the child’s respiratory condition and to guide the physiotherapy intervention. Aim: To assess the intra and inter rater reliability of nasal auscultation, to analyze the relation between sounds’ classification and middle ear’s pressure and compliance as well as with the Clinical Severity Score. Methods: A cross-sectional observational study was composed by 125 nursery children aged up to three years old. Tympanometry, pulmonary and nasal auscultation and application of Clinical Severity Score were performed to each child. Nasal auscultation sounds’ were recorded and sent to 3 blinded experts, that classified, as “obstructed” and “unobstructed”, with a 48 hours interval, in order to analyze inter and intra rater reliability. Results: Nasal auscultation revealed a substantial inter and intra rater reliability (=0,749 and evaluator A - K= 0,691; evaluator B - K= 0,605 and evaluator C - K= 0,724, respectively). Both ears’ pressure was significantly lower in children with an "unobstructed" nasal sound when compared with an “obstructed” nasal sound (t=-3,599, p<0,001 in left ear; t=-2,258, p=0,026 in right ear). Compliance in both ears was significantly lower in children with an "obstructed" nasal sound when compared with “unobstructed” nasal sound (t=-2,728, p=0,007 in left ear; t=-3,830, p<0,001 in right ear). There was a statistically significant association between sounds’ classification and tympanograms types in both ear’s (=11,437, p=0,003 in left ear; =13,535, p=0,001 in right ear). There was a trend to children with an "unobstructed" nasal sound that had a lower clinical severity score when compared with “obstructed” children. Conclusion: It was observed a good intra and substantial inter reliability for nasal auscultation. Nasal auscultation sounds’ classification was related to middle ears’ pressure and compliance.

Literature, translation and national identity: Christina Rossetti and Rosalía de Castro in the work of Plácido Castro

Plácido Castro‘s work has aroused our interest, because it evolves around the question of Galician personality and identity. While working as a journalist and a translator or while writing essays on different literary issues, Plácido Castro has never forgotten his roots or his nation. One could even say that his whole life turns around Galicia. Our purpose is to make a critical analysis of his work, especially as a translator, and try to show how he used translation in order to develop national conscience and identity and to see how far his ideology interfered in the interpretation and translation of Rossetti‘s poetry, in which he found a great similarity with Rosalìa de Castro‘s work.

Self-similarity principle: the reduced description of randomness

A new general fitting method based on the Self-Similar (SS) organization of random sequences is presented. The proposed analytical function helps to fit the response of many complex systems when their recorded data form a self-similar curve. The verified SS principle opens new possibilities for the fitting of economical, meteorological and other complex data when the mathematical model is absent but the reduced description in terms of some universal set of the fitting parameters is necessary. This fitting function is verified on economical (price of a commodity versus time) and weather (the Earth’s mean temperature surface data versus time) and for these nontrivial cases it becomes possible to receive a very good fit of initial data set. The general conditions of application of this fitting method describing the response of many complex systems and the forecast possibilities are discussed.

Double power laws, fractals and self-similarity

Power law (PL) distributions have been largely reported in the modeling of distinct real phenomena and have been associated with fractal structures and self-similar systems. In this paper, we analyze real data that follows a PL and a double PL behavior and verify the relation between the PL coefficient and the capacity dimension of known fractals. It is to be proved a method that translates PLs coefficients into capacity dimension of fractals of any real data.

Double power laws, fractals and self-similarity

Power law (PL) distributions have been largely reported in the modeling of distinct real phenomena and have been associated with fractal structures and self-similar systems. In this paper, we analyze real data that follows a PL and a double PL behavior and verify the relation between the PL coefficient and the capacity dimension of known fractals. It is to be proved a method that translates PLs coefficients into capacity dimension of fractals of any real data.

Power Law Behavior and Self-similarity in Modern Industrial Accidents

Advances in technology have produced more and more intricate industrial systems, such as nuclear power plants, chemical centers and petroleum platforms. Such complex plants exhibit multiple interactions among smaller units and human operators, rising potentially disastrous failure, which can propagate across subsystem boundaries. This paper analyzes industrial accident data-series in the perspective of statistical physics and dynamical systems. Global data is collected from the Emergency Events Database (EM-DAT) during the time period from year 1903 up to 2012. The statistical distributions of the number of fatalities caused by industrial accidents reveal Power Law (PL) behavior. We analyze the evolution of the PL parameters over time and observe a remarkable increment in the PL exponent during the last years. PL behavior allows prediction by extrapolation over a wide range of scales. In a complementary line of thought, we compare the data using appropriate indices and use different visualization techniques to correlate and to extract relationships among industrial accident events. This study contributes to better understand the complexity of modern industrial accidents and their ruling principles.

Three essays on the term structure of interest rates

A PhD Dissertation, presented as part of the requirements for the Degree of Doctor of Philosophy from the NOVA - School of Business and Economics

Structured products in the current low interest rate environment

Directed Research Internship

The determinants of net interest margins & net interest spreads in the Russian & Japanese Commercial Banking sectors

This study presents an empirical investigation of the determinants of net interest margins and spreads in the Russian and Japanese banking sectors with a particular focus on commercial banks. Net interest mar-gins and spreads serve as indicators of financial intermediation efficiency. This paper employed a bank-level unbalanced panel dataset prolonging from 2005 to 2014. My main empirical results show that bank characteristics explain the most of the variation in not only net interest margins but also in spreads. Capi-talization, liquidity risk, inflation, economic growth, private and government debt are important determi-nants of margin in Russia. In Japan to the contrary loan and deposit market concentration along with bank size do predominate. Common significant variables in both countries are the substitution effect, cost effi-ciency and profitability. Turning to net interest spreads, micro- and macro-specific variables are the main significant drivers in Russia. I reach the conclusion that there are no significant determinants of net interest spreads in Japan within the original selection of variables, but operating efficiency and deposits to total funding seem to prevail. In both countries, there are solid differences in the net interest margins as well as spreads once the pre- and the post-crisis periods are considered.

O serviço fiscal aduaneiro criminal e contraordenacional da GNR

At a time of global economic instability, to which Portugal is not oblivious, and aware that the main source of Portuguese State revenue relies on the collection of tribute, the National Republican Guard holds within its mission relevant assignments to the protection of the financial interests of the country, in particular, fiscal and customs. These assignments were inherited from the century - old institution Guarda Fiscal - with evidence given in this domain, which was integrated into the National Republican Guard in 1993, to adopt, a 1St model, that held a specialized unit – Brigada Fiscal, with surveillance and patrolling missions of costa and fiscal and customs supervision, throughout the national territory and maritime zone of respect. In 2009, the result of political decisions, reorganization the State's central administration, appears de 2Nd model, because the Brigada Fiscal assignments were divided by two specialized units - UAF with investigation skills, and UCC for patrolling and surveillance of the coast. Analyzed the legal spectrum of special legislation leading the criminal and transgression sector punitive (RGIT), in essence, is in the UAF that resides the role assignments from the scope of the investigation and supervision of goods in the national territory on a par with the tax authority. Tax inspection assignments, fiscal and customs of the National Republican Guard, are unmatched in the National Tribute System, constituting itself as a potentiality of this special body, in similarity of their counterparts - Spain and Italy; however, have some constraints, that urge to clarify and repair. Foreseeing the future, face the announced news of a new restructuring, on behalf of the interests of the country, and in order to raise the quality of performance of the tax inspection, fiscal and customs, the National Republican Guard shall maintain a model based on the experience already accumulated, obviously adapted to the new demands of a changing society. Despite the current model gain in efficiency, loses in effectiveness. However, the efficiency of a model, without the necessary resources, can never bring “the letter to Garcia” against any kind of infringements, criminal or transgressions. Unless better opinion, both tax structures of the National Republican Guard are valid as an instrument for the prevention and combat of these illegal types. Because they are strategic in pursuing the public interest, given the scarce resources of the country and be the National Republican Guard, the force with the means and know-how of this nature. The political power has the final word.