Charged pullulan derivatives for the development of nanocarriers by polyelectrolyte complexation

Pullulan, a neutral polysaccharide, was chemically modified in order to obtain two charged derivatives: reaction with SO3(.)DMF complex afforded a sulfate derivative (SP), while reaction with glycidyltrimethylammonium chloride gave a quaternary ammonium salt (AP). The presence of the charged groups was confirmed by FTIR. Assessment of the positions where the reaction took place was based on (1)H- and (13)C NMR (COSY, HSQC-TOCSY, HSQC-DEPT, and HMBC) experiments. Estimation of the degree of substitution (DS) was made from elemental analysis data, and further confirmed by NMR peak areas in the case of AP. These new derivatives showed the capability to condense with each other, forming nanoparticles with the ability to associate a model protein (BSA) and displaying adequate size for drug delivery applications, therefore making them good candidates for the production of pullulan-based nanocarriers by polyelectrolyte complexation.

Rs266882 polymorphism analysis in KLK3 gene by RFLPPCR in cases of prostate cancer

Poster presented at the From Basic Sciences to Clinical Research - First International Congress of CiiEM. Egas Moniz, Caparica, Portugal, 27-28 November 2015

Structural and mechanical properties of La0.6Sr0.4M0.1Fe0.9O3-δ (M: Co, Ni and Cu) perovskites

La0.6Sr0.4M0.1Fe0.9O3-δ (M: Co, Ni and Cu) perovskite nanostructures were synthesized using low frequency ultrasound assisted synthesis technique and effect of substitution of Fe by Co, Ni and Cu on crystal structure and mechanical properties in La0.6Sr0.4FeO3-δ perovskite were studied. The HRTEM and Rietveld refinement analyses revealed the uniform equi-axial shape of the obtained nanostructures with the existence of La0.6Sr0.4M0.1Fe0.9O3−δ with mixed rhombohedral and orthorhombic structures. Substitution of Cu decreases the melting point of La0.6Sr0.4FeO3-δ. The results of mechanical characterizations show that La0.6Sr0.4Co0.1Fe0.9O3−δ and La0.6Sr0.4Ni0.1Fe0.9O3−δ have ferroelastic behavior and comparable elastic moduli, however, subtitution of Ni shows higher hardness and lower fracture toughness than Co in Bsite doping

Ligand-Free Palladium-Catalyzed Oxyarylation of Dihydronaphthal­enes and Chromenequinone with o-Iodophenols and 3-Iodolawsone in PEG-400: An Efficient Synthesis of 5-Carbapterocarpans and Pterocarpanquinones

Dihydronaphthalenes were oxyarylated with o-iodophenols, in PEG-400 at 140 or 170 °C, leading regio- and stereoselectively to 5-carbapterocarpans. By using Pd(OAc)2 (5–10 mol%) as precatalyst and Ag2CO3 (1.1 equiv) as base (conditions A), products were obtained in good to excellent chemical yields, in 5–30 minutes, irrespective of the pattern of substitution the starting materials. Alternatively, when p-hydroxyacetophenone oxime derived palladacycle (1 mol%) was used as precatalyst, and dicyclohexylamine (2 equiv) was used as base (silver-free, conditions B), the corresponding adducts were obtained in moderate to good yields, in 0.5 to 4 hours. Finally, the oxyarylation of dihydronaphthalenes­ and chromenquinone with o-iodophenols and 3-iodolawsone in PEG-400 under conditions A led regio- and stereoselectively to the formation of carbapterocarpanquinones and pterocarpanquinones in moderate yield.

The application of symphytosociology in landscape architecture in the Western Mediterranean

This essay addresses the application of indigenous plants in Landscape Architecture projects, based on studies carried out in the field of phytosociology and sinphytosociology. Through this knowledge, it is possible to increase and improve the use of indigenous plants in Projects, aiming at the preservation of biodiversity. Thus, to better understand the western Mediterranean territory, we present a brief biophysical characterization, in which we point out the main factors which contribute to the ground coverage’s distribution in the landscape, namely, concerning climate (oceanity, ombroclimate and thermoclimate) and substrate (geology and lithology). In view of the high level of uniqueness of the identified conditions, a synthesis of the potential main existing climatophilous woods is carried out, regarding sinphytosocialogical class/order, furthermore, pointing out, the main serial stages, their vegetation bioindicators and the ecological peculiarities of each stage (regressive or progressive). Therefore, based on the study area, we point out the vegetation bioindicator’s value as a work tool during analysis, thus allowing us to understand the existing edaphoclimatic conditions, as well as to elaborate a quick diagnosis of each potential climatophilous vegetation series. Moreover, based on the main stages of substitution, it is also possible to identify the presence of endemic plants, or under protection status, and finally, the conservation state of the study area. Further ahead, in project proposal phase, based on information gathered previously, we point out the possibility of elaborating a list of plants correctly adapted to the existing mesologicall conditions. Thus, within each serial stage, the necessary ecological conditions for a correct adaption of the vegetation material are referred, therefore, avoiding possible limiting factors to their development, such as precipitation, soil erosion, light availability, salinity, among many others. Lastly, some considerations are made about the main ideas that should be remembered throughout this essay, namely, regarding the importance of the use of sinphytosociology’s knowledge as an analysis tool, as well as of high interest for the elaboration of proposals which aim at the floristic heritage’s conservation and the landscape’s scenic quality. Ce travail traite de l`application de plantes autochtones dans des projets d`Architecture Paysagiste ayant pour base des études réalisées dans le cadre de la phytosociologie et Symphytosociologie. À travers ces connaissances, il est possible d`incrémenter et améliorer l`utilisation de plantes autochtones dans les Projets basés sur la conservation de la biodiversité. Ainsi, afin de mieux comprendre le territorie de la méditérrannée occidentale, on présente une brève caractérisation biophysique, dans laquelle nous soulignons les principaux facteurs qui contribuent à la répartition de la végétation dans le paysage, notamment au niveau climatique (l`océanité, ombrothermique et thermoclimatique) et du substrat (géologie et lithologie). Face aux conditions, identifiées ci-dessus, élévées en originalité, il est utile d`élaborer une synthèse des principaux bois potentiels climatophiles existants au niveau de la classe/ordre symphitosociologique, en soulignant également les principales étapes de série, leurs bioindicateurs végétaux et aux particularités écologiques de chaque étape (régressive ou progressive). Ainsi, sur la base de l`interprétation de la zone d`étude, le bioindicateur végétal se distingue comme un outil de travail durant l`analyse, permettant de cette façon comprendre les conditions édapho-climatiques existantes, ainsi comme élaborer un rapide diagnostic de chaque série de végétation potentielle climatophile. En outre, sur la base des principales étapes de remplacement, il est également possible d`identifier la présence de plantes endémiques, ou avec un statut de protection et enfin l`état de conservation de la zone d`étude. Déjà au stade de proposition du projet, basée sur l`information recueillie précédemment, il y a la possibilité d`établir une liste de plantes bien adaptées aux conditions mésologiques. Ainsi, dans chaque étape de série, les conditions écologiques nécessaires à une bonne adaptation de la matière végétale sont référées, évitant ainsi des facteurs limitant à son développement, tels que les précipitations, l`érosion des soís, disponibilité de la lumière, de la salinité, parmi beaucoup d`autres. Et enfin, quelques considérations se tissent sur les principales idées à retenir tout au long du travail, notamment l`importance d`utiliser la connaissance de la symphytosociologie comme un outil d`analyse d`un grand intérêt pour la développement de propositions pour la conservation du patrimoine floristique et la qualité pittoresque du paysage.

Impact of Public Debt on Economic Growth in Advanced Economies

This paper examines the impact of public debt on the economic growth in advanced economies over a period of 1946 to 2009, using an econometric approach. The findings suggested an inverse relationship between public debt and economic growth in advanced economies. These relationships were found to be significant as well. Model results also show that the real GDP growth rate does not decline sharply whether the public debt-to-GDP ratio is lower than 220%. The public debt-to-GDP ratio elasticity of the real growth rate shows that an increase of 1% in public debt/GDP category above 120% decreases the real GDP growth rate in 1.13%. The negative effect of public debt is only stronger on the real GDP growth rate in advanced economies when the public debt-to-GDP ratio is above 220%. Finally, these findings lead us to reassess the austerity agenda, and the governments should devise new strategies for public debt management in advanced economies, taking into account their economic and financial performance.

Development and chemo-mechanical characterization of eco-compatible extenders containing REOB and recycled tyres’ rubber for the production of greener bituminous binders

The concepts of circular economy and sustainability are the basis of the present experimental research that seeks to reduce the environmental impact of traditional road construction materials. This study mainly focuses on the development and the chemo-mechanical characterization of bitumen extenders containing rubber (R) from end-of-life tyres (ELTs) and re-refined engine oil bottoms (REOBs) for the production of innovative and eco-friendly extended bitumens (i.e. bituminous binders containing 25%wt. of recycled products) and asphalt mixtures. In order to create more sustainable asphalt mixes, also recycled aggregates are used for partial replacement of virgin natural aggregates in the aggregate skeleton. The experimental program encompassed five successive steps: (i) the evaluation of physicochemical properties of R and REOB, (ii) the definition of the optimal extenders by the development of a new protocol and their characterizations, (iii) the realization and investigation of the chemo-rheological responses of the extended bitumens at different boundary conditions, (iv) the assessment of the effectiveness of analytical method to predict the rheological parameters of extended bitumens and, finally, (v) the analysis of the mechanical performances of the corresponding asphalt mixtures. A standard 50/70 penetration grade bitumen was chosen as a reference material and the main constituent of the innovative bituminous products. The results of this study underlined the importance of material characterization. The incorporation of R-REOB extenders strongly affects the chemo-rheological responses of the resulting extended bitumens and asphalt mixtures overall the boundary conditions. While the presence of R and the consequent formation of a polymer network improves the elasticity of the final products, especially at high test temperatures; the addition of REOB, softens the bituminous binders and asphalt mixes increasing their response at low test temperatures. Nonetheless, the use of recycled products increased the susceptibility of bituminous material under damaging conditions, which would need further investigations.

RICORDACI: Research on the Conservation, Restoration and Diagnosis of Cinematographic Films

This thesis is the result of the RICORDACI project, a three-year European-funded initiative involving the collaboration between the University of Bologna and the restoration laboratory of the Cineteca di Bologna, L'immagine Ritrovata, which aimed to develop innovative solutions and technologies for the preservation of cinematographic film heritage. In particular, this thesis presents new analytical methodologies to exploit two types of portable miniaturized Near Infrared spectrometers working in Diffuse Reflectance over the Short Wave Infrared (SWIR) range, to study the near infrared (NIR) spectral behavior of film base materials for an accurate, non-invasive and fast characterization of the polymer type; and for films with cellulose acetate supports, they can be employed as a diagnostic tool for monitoring the Degree of substitution (DS) affected by the loss of acetyl groups. The proposed methods offer non-invasive, fast, inexpensive and simple alternatives for the characterization and diagnosis of film bases to help the strategic planning and decision-making regarding storage, digitalization and intervention of film collections. Secondly, the thesis includes the evaluation of new green cleaning systems and solvents for the effective, fast and innocuous removal of undesired substances from degraded cinematographic films bases; these tests compared the efficiency of traditional systems and solvents against the new proposals. Firstly, the use of Deep Eutectic Solvent formulations for removing softened gelatin residues from cellulose nitrate bases; and secondly, the employment of green volatile solvents with different application methods, including the use of new electrospun nylon mats, for avoiding the dangerous use of friction for the removal of Triphenyl Phosphate blooms from the surface of cellulose acetate bases. The results obtained will help improving the efficiency of the interventions needed before the digitalization of historical cinematographic films and will pave the way for further investigation on the use of green solvents for cleaning polymeric heritage objects.

Agregação de cadeias de acetatos de celulose em LiCl/DMAc: avaliação via viscosimetria

Celulose de linter foi acetilada, visando obter acetatos de celulose com diferentes Graus de Substituição (GS) em meio homogêneo, usando cloreto de lítio/N,N-dimetilacetamida (LiCl/DMAc) como sistema de solvente, e anidrido acético como reagente acetilante. A agregação entre cadeias de celulose ou acetatos de celulose (GS 0,8, 1,5 e 2,0) em solução foi avaliada através de medidas viscosimétricas. Os resultados mostraram que a formação de agregados no sistema de solvente utilizado (LiCl/DMAc) é diferente para celulose e acetatos, e dependente da temperatura e do GS, no caso dos acetatos. Este trabalho corresponde à primeira etapa de um estudo em que se pretende preparar filmes de acetatos, assim como de acetatos reforçados com celulose, diretamente a partir de soluções destes em LiCl/DMAc. Os resultados apresentados permitem uma escolha melhor embasada do intervalo de concentração mais adequado para preparação de filmes, a partir de soluções de acetatos e celulose nesse sistema de solvente.

Sisal cellulose acetates obtained from heterogeneous reactions

In the present work, cellulose obtained from sisal, which is a source of rapid growth, was used. Cellulose acetates were produced in heterogeneous medium, using acetic anhydride as esterifying agent and iodine as catalyst, to check if the procedure described in the literature for commercial cellulose also is adequate to sisal cellulose. The results indicated that iodine is an excellent catalyst to obtain sisal cellulose acetates, but the reaction is so fast as described in the literature when, instead of sisal, lower average molar weight cellulose (microcrystalline) is used. The crystallinity index (I(c)) of sisal cellulose acetates diminished compared to sisal cellulose, but there was no direct correlation between their degree of substitution (DS) and I(c). Probably acetyl groups were introduced more homogeneously along the short chains of microcrystalline cellulose, when compared to sisal cellulose, and then for microcrystalline cellulose acetates the Ic decreases as DS increases. Using the linear correlation that was found between degree of substitution (DS) and time reaction is possible to control the DS of sisal cellulose acetates, considering a large interval of degrees of substitution (0.3-2.8).

Income inequality and pecuniary crimes

This paper verifies the relationship between income inequality and pecuniary crimes. The elasticity of pecuniary crimes relative to inequality is 1.46, corroborating previous literature. Other factors important to decrease criminality are expanding job opportunities and a more efficient legal system, (C) 2009 Elsevier B.V. All rights reserved.

The Qu-Prolog unification algorithm: Formalisation and correctness

Qu-Prolog is an extension of Prolog which performs meta-level computations over object languages, such as predicate calculi and lambda-calculi, which have object-level variables, and quantifier or binding symbols creating local scopes for those variables. As in Prolog, the instantiable (meta-level) variables of Qu-Prolog range over object-level terms, and in addition other Qu-Prolog syntax denotes the various components of the object-level syntax, including object-level variables. Further, the meta-level operation of substitution into object-level terms is directly represented by appropriate Qu-Prolog syntax. Again as in Prolog, the driving mechanism in Qu-Prolog computation is a form of unification, but this is substantially more complex than for Prolog because of Qu-Prolog's greater generality, and especially because substitution operations are evaluated during unification. In this paper, the Qu-Prolog unification algorithm is specified, formalised and proved correct. Further, the analysis of the algorithm is carried out in a frame-work which straightforwardly allows the 'completeness' of the algorithm to be proved: though fully explicit answers to unification problems are not always provided, no information is lost in the unification process.

Intralesional pentoxifylline as an adjuvant treatment for perioral post-burn hypertrophic scars

Pentoxifylline (PTF), a methylxanthine derivative, has therapeutic use as an antifibrotic agent. In vitro, PTF inhibits the production of collagen and reduces the proliferation of fibroblasts in hypertrophic scars. This study aimed to evaluate changes in the elasticity of hypertrophic scars in the peribuccal area in burned patients, who presented with mouth-opening limitation. Eighteen patients were divided into two groups. The case group (n = 10) was treated with PTF 1 mg ml(-1), while in the control group (n = 8) no treatment was performed. Measurements of mouth opening (lip-to-lip and tooth-to-tooth distances in mm) were taken, before and after five therapeutic sessions with pentoxifylline with weekly intervals. The variations of these measures (Delta%) were calculated and submitted to statistical analyses. There was a significant improvement in the opening of the mouth, in vermilion distance (V = 3.20 mm) as much as the dental distance (DD = 4.19 mm) in the treated group, than in the control group. It was noted that pentoxifylline increases the elasticity of hypertrophic scars in the perioral area. (C) 2009 Elsevier Ltd and ISBI. All rights reserved.

Electrospun silk-elastin-like fiber mats for tissue engineering applications

Protein-based polymers are present in a wide variety of organisms fulfilling structural and mechanical roles. Advances in protein engineering and recombinant DNA technology allow the design and production of recombinant protein-based polymers (rPBPs) with an absolute control of its composition. Although the application of recombinant proteins as biomaterials is still an emerging technology, the possibilities are limitless and far superior to natural or synthetic materials, as the complexity of the structural design can be fully customized. In this work, we report the electrospinning of two new genetically engineered silk-elastin-like proteins (SELPs) consisting of alternate silk- and elastin-like blocks. Electrospinning was performed with formic acid and aqueous solutions at different concentrations without addition of further agents. The size and morphology of the electrospun structures was characterized by scanning electron microscopy showing to be dependent of concentration and solvent used. Treatment with air saturated with methanol was employed to stabilize the structure and promote water insolubility through a time-dependent conversion of random coils into β-sheets (FTIR). The resultant methanol-treated electrospun mats were characterized for swelling degree (570-720%), water vapour transmission rate (1083 g/m2/day) and mechanical properties (modulus of elasticity of ~126 MPa). Furthermore, the methanol-treated SELP fiber mats showed no cytotoxicity and were able to support adhesion and proliferation of normal human skin fibroblasts. Adhesion was characterized by a filopodia-mediated mechanism. These results demonstrate that SELP fiber mats can provide promising solutions for the development of novel biomaterials suitable for tissue engineering applications.

A real time pricing approach to deal with excessive wind power situations

The introduction of wind power generation in several countries around the world, including in European countries, where energy policy directives have encouraged the use of renewables, led to several changes in market and power systems operation. The intensive integration of these sources has led to situations in which the demand is lower than the available renewable resources. In these situations a part of the available generation is wasted if not used for storage or to supply additional demand. This paper proposes a real time demand response methodology based on changing the electricity price for the consumers expecting an increase in the demand in the periods in which that demand is lower than the available renewable generation. The consumers response to the changes in electricity price is characterized by their price elasticity of demand considered distinct for each consumer type. The proposed methodology is applied to the Portuguese power system, in the context of the Iberian electricity market (MIBEL). The renewable-based producers are considered as special producers, with special tariffs, and so it is important to use the energy available as it will be paid anyway. In this context, consumers are entities actively participating in the operation of the market.