Mechanical characterization of polyhydroxyalkanoate and poly (lactic acid) blends

In this work, the mechanical behavior of polyhyroxyalkanoate (PHA)/poly(lactic acid) (PLA) blends is investigated in a wide range of compositions. The mechanical properties can be optimized by varying the PHA contents of the blend. The flexural and tensile properties were estimated by different models: the rule of mixtures, Kerner–Uemura–Takayanagi (KUT) model, Nicolai–Narkis model and Béla–Pukánsky model. This study was aimed at investigating the adhesion between the two material phases. The results anticipate a good adhesion between both phases. Nevertheless, for low levels of incorporation of PHA (up to 30%), where PLA is expectantly the matrix, the experimental data seem to deviate from the perfect adhesion models, suggesting a decrease in the adhesion between both polymeric phases when PHA is the disperse phase. For the tensile modulus, a linear relationship is found, following the rules of mixtures (or a KUT model with perfect adhesion between phases) denoting a good adhesion between the phases over the composition range. The incorporation of PHA in the blend leads to a decrease in the flexural modulus but, at the same time, increases the tensile modulus. The impact energy of the blends varies more than 157% over the entire composition. For blends with PHA weight fraction lower than 50%, the impact strength of the blend is higher than the pure base polymers. The highest synergetic effect is found when the PLA is the matrix and the PHA is the disperse phase for the blend PHA/PLA of 30/70. The second maximum is found for the inverse composition of 70/30. PLA has a heat-deflection temperature (HDT) substantially lower than PHA. For the blends, the HDT increases with the increment in the percentage of the incorporation of PHA. With up to 50% PHA (PLA as matrix), the HDT is practically constant and equal to PLA value. Above this point (PHA matrix), the HDT of the polymer blends increases linearly with the percentage of addition of PHA.

La social stock exchange au Portugal: un nouvel allié de l'économie sociale

Résumé Cet article vise à contribuer à la connaissance de la Bolsa de Valores Sociais (BVS) — Social Stock Exchange — récemment créé au Portugal, dont le but primatial était de permettre la prise de moyens de financement des entités de l'Économie Sociale engagées dans des projets d'éducation et d'entreprenariat. Il se penchera sur la qualification juridique des divers types d'entités cotées dans la BVS, sur le concept d'investisseur social et sur la protection dont il jouira, vis-à-vis des exigences de transparence et de gouvernance qui incombent à ces entités. Le thème proposé sera examiné en soulignant les virtualités et le potentiel de la BVS, faisant référence à l'un ou à l'autre sujet qui viennent à effet, avec un accent particulier sur l'avantage d'élaborer un code de gouvernance corporative pour les entités de l'Économie Sociale. Abstract This article aims to contribute to the knowledge of the Bolsa de Valores Sociais (BVS) — Social Stock Exchange — recently created in Portugal, whose primatial purpose was to allow the taking of means of financing the Social Economy entities, engaged in projects in education and entrepreneurship. It will reflect on the legal classification of the various types of entities rated in the BVS, on the concept of social investor and on the protection he will enjoy, leading to the consequent demands for transparency and governance that falls upon those entities. The proposed theme will be discussed highlighting the virtues and potential of BVS, playing in one or two topics that comes to purpose, with particular emphasis on the relevance of drawing up a code of corporate governance for entities of the Social Economy. Resumen Este artículo tiene como objetivo contribuir al conocimiento de la Bolsa de Valores Sociales (BVS), recientemente creada en Portugal, cuya finalidad principal es que las entidades de la economía social dedicadas a proyectos en las áreas de educación y de iniciativa empresarial puedan obtener medios financieros. Se abordará la calificación jurídica de los diversos tipos de entidades que cotizan en la BVS, así como el concepto de inversor social y la protección de que éste goza, con las consiguientes exigencias en materia de transparencia y de gobierno que recaen sobre esas entidades. Se analizará la temática propuesta destacando las virtudes y potencialidades de la BVS, sin omitir algún otro tópico adyacente que resulte relevante, en especial la conveniencia de que sea elaborado un código de gobernanza corporativa para las entidades de la economía social.

Le rôle de l'intrigue du sérail dans les lettres persanes de Montesquieu

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Electroanalysis of urinary L-dopa using tyrosinase immobilized on gold nanoelectrode ensembles

The performance of an amperometric biosensor constructed by associating tyrosinase (Tyr) enzyme with the advantages of a 3D gold nanoelectrode ensemble (GNEE) is evaluated in a flow-injection analysis (FIA) system for the analysis of l-dopa. GNEEs were fabricated by electroless deposition of the metal within the pores of polycarbonate track-etched membranes. A simple solvent etching procedure based on the solubility of polycarbonate membranes is adopted for the fabrication of the 3D GNEE. Afterward, enzyme was immobilized onto preformed self-assembled monolayers of cysteamine on the 3D GNEEs (GNEE-Tyr) via cross-linking with glutaraldehyde. The experimental conditions of the FIA system, such as the detection potential (−0.200 V vs. Ag/AgCl) and flow rates (1.0 mL min−1) were optimized. Analytical responses for l-dopa were obtained in a wide concentration range between 1 × 10−8 mol L−1 and 1 × 10−2 mol L−1. The limit of quantification was found to be 1 × 10−8 mol L−1 with a resultant % RSD of 7.23% (n = 5). The limit of detection was found to be 1 × 10−9 mol L−1 (S/N = 3). The common interfering compounds, namely glucose (10 mmol L−1), ascorbic acid (10 mmol L−1), and urea (10 mmol L−1), were studied. The recovery of l-dopa (1 × 10−7 mol L−1) from spiked urine samples was found to be 96%. Therefore, the developed method is adequate to be applied in the clinical analysis.

Layer-by-layer immobilization of carbon dots fluorescent nanomaterials on single optical fiber

We report within this paper the development of a fiber-optic based sensor for Hg(II) ions. Fluorescent carbon nanoparticles were synthesized by laser ablation and functionalized with PEG200 and N-acetyl-l-cysteine so they can be anionic in nature. This characteristic facilitated their deposition by the layer-by-layer assembly method into thin alternating films along with a cationic polyelectrolyte, poly(ethyleneimine). Such films could be immobilized onto the tip of a glass optical fiber, allowing the construction of an optical fluorescence sensor. When immobilized on the fiber-optic tip, the resultant sensor was capable of selectively detecting sub-micromolar concentrations of Hg(II) with an increased sensitivity compared to carbon dot solutions. The fluorescence of the carbon dots was quenched by up to 44% by Hg(II) ions and interference from other metal ions was minimal.

Fin de partie: l'infini recommencement de rien

Dans Fin de partie, Beckett se révèle de nouveau un maître du théâtre de l’âme, mais d’une façon pas du tout conventionnelle. On doit classer cette pièce dans l’antithéâtre parce qu’elle manque d’intrigue, il n’y a que de situations cycliques toujours répétées, le temps ne veut pas passer, c’est plutôt un moment éternel, les personnages manquent de consistance et d’individualité : ils sont davantage des incarnations d’attitudes humaines, et ils parlent un langage décousu, un bourdonnement dépourvu de sens. Bien que tous ces aspects contribuent à l’ambiguïté de la pièce, rien n’y est laissé au hasard : tout sert à communiquer l’incommunicable. La scène se passe dans un lieu clos, avec une lumière crépusculaire qui suggère la fin du jour. Les personnages et les objets se trouvent dans des poubelles (Nagg et Nell) ou couverts par des draps : peu à peu, les objets et les personnages se dévoilent d’une façon fragmentée. C’est Clov qui nous dit qu’il s’agit de la fin de quelque chose, mais déjà le décor, la lumière, la déchéance physique des personnages et les dialogues à peine esquissés suggèrent un stage final qui n’en finit plus, qui devient un moment éternel, car la mort, elle non plus, ne se présente pas comme une solution pour le problème de notre existence absurde. Et nous voilà de nouveau face à face avec l’absurdité de la condition humaine, où l’homme se sent privé de toute certitude et incapable de découvrir un sens à son existence. Le tragique de la condition humaine, et le désir de lui mettre fin est le fil conducteur de Fin de partie. Les personnages montrent tout au long de la pièce que la condition humaine est intolérable et qu’ils sont écrasés par la routine et l’ennui. Ils se sentent perdus et abandonnés par un dieu quiconque, un monstre qui a créé la nature humaine. La vie est une pile de moments infernaux ; tout le monde est dans l’attente de quelqu’un ou d’un événement qui puisse changer son cours. Mais rien ne change, les personnages sont trop passifs – Clov se prépare pour son voyage, cependant, au lieu de partir, il reste là, immobile, jusqu’à la fin. Mais c’est juste pour ce danger que Beckett veut nous alerter : si nous ne faisons pas usage de notre liberté en nous recréant par une succession de choix, nous serons damnés, c’est-à-dire, condamnés à vivre dans le désespoir, le néant, l’absurde – la vie sera toujours un infini recommencement de rien.

Monitorização de cobre em vinhos verdes

A presente dissertação descreve o desenvolvimento e a caracterização de sensores potenciométricos com base em polímeros de impressão molecular e de sensores ópticos com base em membranas de poli(cloreto de vinilo), PVC, para a determinação de cobre em vinhos verdes. Os sensores potenciométricos foram preparados a partir de diferentes solventes (metanol e clorofórmio), tendo o seu crescimento decorrido na presença ou ausência da molécula molde (cobre). Os sistemas sensores selectivos ao cobre continham partículas de polímeros com ou sem impressão molecular como material electroactivo, dispersas em solvente plastificante, PVC e, em alguns casos, aditivo aniónico. A avaliação dos vários sistemas baseou-se na comparação das características operacionais dos diversos eléctrodos onde foram aplicados. Estas características foram obtidas a partir de curvas de calibração, cujos declives e limites de detecção variaram entre -39,9 – 37,0 mV decada-1 e 4,2 – 29,1 μg mL-1, respectivamente. Os sensores não são independentes do pH uma vez que o complexo formado entre o cobre e a difenilcarbazida é favorecido por valores de pH próximos de 5. Assim, obtiveram-se melhores resultados usando água desionizada ou solução tampão de HEPES revelando-se um método rápido e relativamente eficaz nestas condições. Os sensores ópticos basearam-se na reacção colorimétrica entre o cobre e um complexante. Os reagentes complexantes escolhidos foram a neocuproína, a difenilcarbazida e o dietilditiocarbamato de sódio. Avaliou-se o efeito de vários parâmetros experimentais na resposta destes sensores, tais como o pH (avaliado para os valores 3,00 e 5,00), a concentração de cobre (que variou entre 0,06 e 317,7 mg L- 1) e as próprias características da membrana. Os melhores resultados foram obtidos a pH 3, numa gama de concentrações de 0,06 e 31,8 mg L-1 usando a difenilcarbazida como reagente complexante. A aplicação destes sensores a vinhos requer ainda estudos adicionais, especialmente no que diz respeito à necessidade de implementar algum procedimento de pré-tratamento de amostra.

Simultaneous distillation–extraction of high-value volatile compounds from Cistus ladanifer L.

The present paper describes a procedure to isolate volatiles from rock-rose (Cistus ladanifer L.) using simultaneous distillation–extraction (SDE). High-value volatile compounds (HVVC) were selected and the influence of the extraction conditions investigated. The effect of the solvent nature and extraction time on SDE efficiency was studied. The best performance was achieved with pentane in 1 h operation. The extraction efficiencies ranged from 65% to 85% and the repeatability varied between 4% and 6% (as a CV%). The C. ladanifer SDE extracts were analysed by headspace solid phase microextraction (HS-SPME) followed by gas chromatography with flame ionization detection (GC-FID). The HS-SPME sampling conditions such as fiber coating, temperature, ionic strength and exposure time were optimized. The best results were achieved with an 85 µm polyacrylate fiber for a 60 min headspace extraction at 40ºC with 20% (w/v) of NaCl. For optimized conditions the recovery was in average higher than 90% for all compounds and the intermediate precision ranged from 4 to 9% (as CV %). The volatiles α-pinene (22.2 mg g−1 of extract), 2,2,6-trimethylcyclohexanone (6.1 mg g−1 of extract), borneol (3.0 mg g−1 of extract) and bornyl acetate (3.9 mg g−1 of extract) were identified in the SDE extracts obtained from the fresh plant material.

Chlormequat selective electrodes: construction, evaluation and application at FIA systems

A flow injection analysis (FIA) system having a chlormequat selective electrode is proposed. Several electrodes with poly(vinyl chloride) based membranes were constructed for this purpose. Comparative characterization suggestedthe use of membrane with chlormequat tetraphenylborate and dibutylphthalate. On a single-line FIA set-up, operating with 1x10-2 mol L-1 ionic strength and 6.3 pH, calibration curves presented slopes of 53.6±0.4mV decade-1 within 5.0x10-6 and1.0x10-3 mol L-1, andsquaredcorrelation coefficients >0.9953. The detection limit was 2.2x10-6 mol L-1 and the repeatability equal to ±0.68mV (0.7%). A dual-channel FIA manifold was therefore constructed, enabling automatic attainment of previous ionic strength andpH conditions and thus eliminating sample preparation steps. Slopes of 45.5±0.2mV decade -1 along a concentration range of 8.0x10-6 to 1.0x10-3 mol L-1 with a repeatability ±0.4mV (0.69%) were obtained. Analyses of real samples were performed, and recovery gave results ranging from 96.6 to 101.1%.

Flow injection potentiometric determination of chlorpromazine

New chlorpromazine selective electrodes with a tubular arrangement and no internal reference solution are proposed. Selective membranes are of poly(vinyl chloride) (PVC) with the tetraphenylborate•chlorpromazine (TPB•CPZ) ion-exchanger dissolved in o-nitrophenyl octyl ether (oNPOE). Analytical features of the electrodes were evaluated on a single-channel flow assembly having 500 µl injection volumes and flow-rates of 4.5 ml min−1. For a carrier solution of 3.3×10−3Min sodium sulphate, Nernstian responsewas observed over the concentration range 1.0×10−5 to 1.0×10−2 M. Average slopes were about 59mVdecade−1 and squared correlation coefficients were >0.9984. Slight hiper-Nernstian behaviour was observed in buffer solutions of 4.4 pH; average slopes were of 62.06mVdecade−1. The electrode displayed a good selectivity for CPZ, with respect to, several foreign inorganic and organic species. The selective electrodes were successfully applied to the analysis of pure solutions and pharmaceutical preparations. Proposed method allows the analysis of 84 samples h−1, producing wastewaters of low toxicity. The proposed method offers the advantage of simplicity, accuracy, applicability to coloured and turbid samples, and automation feasibility.