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- Polyoxometalate@Periodic mesoporous organosilicas as active materials for oxidative desulfurization of dieselsPublication . Ribeiro, Susana; Almeida, Pedro L.; Pires, João; De Castro, Baltazar; Balula, SaleteNovel material catalysts based in the active zinc-substituted polyoxotungstate ([PW11Zn(H2O)(39)](5-), abbreviated as PW11Zn) were efficiently used in the oxidative desulfurization of real and model diesels. These active catalytic center was strategically immobilized in a less hydrophilic periodic mesoporous organosilicas (PMOs), containing ethane-bridge (PMOE) and benzene-bridge (PMOB) walls, functionalized with (3-aminopropyl)triethoxysilane (aptes). The efficiency of the novel catalytic composites (PW11Zn@aptesPMOE and PM11Zn@aptesPMOB) was studied under oxidative desulfurization system (CODS) without the presence of an extraction solvent and also using a biphasic (diesel/extraction solvent) oxidative desulfurization system (ECODS). Both composites presented higher desulfurization efficiency under the solvent-free system, reaching ultra-low levels of sulfur compounds after only 1 h and using low ratio of H2O2/S = 4. The catalysts could be recycled without loss of activity for ten consecutive cycles. However, after the first desulfurization cycle complete desulfurization was achieved within only 30 min using PW11Zn@aptesPMOE composite. Also, the structure of PW it Zn@aptesPMOE demonstrated to be more stable than PW11Zn@aptesPMOB, probably due to the occurrence of some PW11Zn leaching from the PMOB surface, probably caused by the lower interaction of PW11Zn with the benzene-bridge PMOB wall. The most robust catalyst PW11Zn@aptesPMOE was used to desulfurize a real diesel achieving 75.9% of desulfurization after 2 h. The catalyst was further recycled with success to treat real diesel.
- Rheo-NMR study of water-based cellulose liquid crystal system at high shear ratesPublication . Echeverria, Coro; Almeida, Pedro L.; Feio, Gabriel; Figueirinhas, João; Rey, Alejandro D.; Godinho, Maria HelenaSince long ago cellulosic lyotropic liquid crystals were thought as potential materials to produce fibers competitive with spidersilk or Kevlar, yet the processing of high modulus materials from cellulose-based precursors was hampered by their complex rheological behavior. In this work, by using the Rheo-NMR technique, which combines deuterium NMR with rheology, we investigate the high shear rate regimes that may be of interest to the industrial processing of these materials. Whereas the low shear rate regimes were already investigated by this technique in different works [1-4], the high shear rates range is still lacking a detailed study. This work focuses on the orientational order in the system both under shear and subsequent relaxation process arising after shear cessation through the analysis of deuterium spectra from the deuterated solvent water. At the analyzed shear rates the cholesteric order is suppressed and a flow-aligned nematic is observed which for the higher shear rates develops after certain time periodic perturbations that transiently annihilate the order in the system. During relaxation the flow aligned nematic starts losing order due to the onset of the cholesteric helices leading to a period of very low order where cholesteric helices with different orientations are forming from the aligned nematic, followed in the final stage by an increase in order at long relaxation times corresponding to the development of aligned cholesteric domains. This study sheds light on the complex rheological behavior of chiral nematic cellulose-based systems and opens ways to improve its processing. (C) 2015 Elsevier Ltd. All rights reserved.
- Perspectives on the electrically induced properties of electrospun cellulose/liquid crystal devicesPublication . Rosu, C.; MANAILA MAXIMEAN, DOINA; Kundu, S.; Almeida, Pedro L.; Danila, O.A mat of electrospun cellulose fibers are deposed on transparent conductive oxide covered glass, and two such plates enclose a nematic liquid crystal. Thus two new types of Cellulose based Polymer Dispersed Liquid Crystal devices, based on hydroxypropylcellulose and Cellulose Acetate and the nematic liquid crystal E7 have been obtained. The current-voltage characteristics indicates ionic type conduction. Heating-cooling cycles have been applied on the samples and the activation energies have been determined. Simultaneously with the thermo-stimulated currents, the optical transmission dependence on the d.c. electric field and temperature was registered. ON-OFF switching times have been determined for different control voltages. (C) 2011 Elsevier B.V. All rights reserved.
- Real-time rheology of actively growing bacteriaPublication . Portela, R.; Almeida, Pedro L.; Patricio, Pedro; Cidade, T.; Sobral, R. G.; R. Leal, CatarinaThe population growth of a Staphylococcus aureus culture, an active colloidal system of spherical cells, was followed by rheological measurements, under steady-state and oscillatory shear flows. We observed a rich viscoelastic behavior as a consequence of the bacteria activity, namely, of their multiplication and density-dependent aggregation properties. In the early stages of growth (lag and exponential phases), the viscosity increases by about a factor of 20, presenting several drops and full recoveries. This allows us to evoke the existence of a percolation phenomenon. Remarkably, as the bacteria reach their late phase of development, in which the population stabilizes, the viscosity returns close to its initial value. Most probably, this is caused by a change in the bacteria physiological activity and in particular, by the decrease of their adhesion properties. The viscous and elastic moduli exhibit power-law behaviors compatible with the "soft glassy materials" model, whose exponents are dependent on the bacteria growth stage. DOI: 10.1103/PhysRevE.87.030701.
- On the influence of imidazolium ionic liquids on cellulose derived polymersPublication . Paiva, Tiago; Echeverria Zabala, Coro; Godinho, Maria Helena; Almeida, Pedro L.; Corvo, Marta C.The demand for better cellulose solvents has driven the search for new and improved materials to enable the processing of this polysaccharide. Ionic liquids have been debated for a long time as interesting alternatives, but the molecular details on the solubilization mechanism have been a matter of controversy. Herein, for the first time, the structure and dynamics of hydroxypropylcellulose (HPC) liquid crystal solutions were probed in the presence of imidazolium ionic liquids (ILs), conjugating rheological measurements with magnetic resonance spectroscopy. This study provides a characterization of the solutions macroscopic behaviour, where the liquid crystalline (LC) properties were maintained. Using ILs with different side chain lengths, the influence of the hydrophobic IL domain in the solvation abilities of ILs towards a cellulose derived polymer was accessed, providing experimental evidence on these interactions.
- Spotting plants' microfilament morphologies and nanostructuresPublication . Almeida, Ana; Canejo, João; Mur, Urban; Copar, Simon; Almeida, Pedro L.; Zumer, Slobodan; Godinho, Maria HelenaThe tracheary system of plant leaves is composed of a cellulose skeleton with diverse hierarchical structures. It is built of polygonally bent helical microfilaments of cellulose-based nanostructures coated by different layers, which provide them high compression resistance, elasticity, and roughness. Their function includes the transport of water and nutrients from the roots to the leaves. Unveiling details about local interactions of tracheary elements with surrounding material, which varies between plants due to adaptation to different environments, is crucial for understanding ascending fluid transport and for tracheary mechanical strength relevant to potential applications. Here we show that plant tracheary microfilaments, collected from Agapanthus africanus and Ornithogalum thyrsoides leaves, have different surface morphologies, revealed by nematic liquid crystal droplets. This results in diverse interactions among microfilaments and with the environment; the differences translate to diverse mechanical properties of entangled microfilaments and their potential applications. The presented study also introduces routes for accurate characterization of plants' microfilaments.
- Living S. aureus bacteria rheologyPublication . Portela, R.; Franco, J. M.; Patricio, Pedro; Almeida, Pedro L.; Sobral, R. G.; Leal, Catarina R.The rheological characterization of Staphylococcus aureus cultures has shown a complex and rich viscoelastic behavior, during the bacteria population growth, when subject to a shear flow [1,2]. In particular, in stationary shear flow, the viscosity keeps increasing during the exponential phase reaching a maximum value (∼30x the initial value) after which it drops and returns close to its initial value in the stationary phase of growth, where the cell number of the bacterial population stabilizes. These behaviors can be associated with cell density and aggregation patterns that are developed during culture growth, showing a collective behavior. This behavior has no counterpart in the bacterial growth curve obtained by optical density monitorization (OD620nm and cfus/ml measurements). In oscillatory flow, the elastic and viscous moduli exhibit power-law behaviors whose exponents are dependent on the bacteria growth stage. These power-law dependencies of G’ and G’’ are in accordance with the Soft Glassy Material model [3], given by: G’~ ωx and G’’~ ωx To describe the observed behavior, a microscopic model considering the formation of a dynamic web-like structure was hypothesized [1], where percolation phenomena can occur, depending on the growth stage and on cell density. Recently, using real-time image rheology was possible to visualize the aggregation process associated with these dramatic changes in the viscoelastic behavior. In particular, the formation of web-like structures, at a specific time interval during the exponential phase of the bacteria growth and the cell sedimentation and subsequent enlargement of bacterial aggregates in the passage to the stationary phase of growth. These findings were essential to corroborate the microscopic model previously proposed and the main results of this study are compiled and presented in this work, see Fig.1.
- Bacterial cellulose: a versatile biopolymer for wound dressing applicationsPublication . Portela, Raquel; R. Leal, Catarina; Almeida, Pedro L.; Sobral, RitaAlthough several therapeutic approaches are available for wound and burn treatment and much progress has been made in this area, room for improvement still exists, driven by the urgent need of better strategies to accelerate wound healing and recovery, mostly for cases of severe burned patients. Bacterial cellulose (BC) is a biopolymer produced by bacteria with several advantages over vegetal cellulose, such as purity, high porosity, permeability to liquid and gases, elevated water uptake capacity and mechanical robustness. Besides its biocompatibility, BC can be modified in order to acquire antibacterial response and possible local drug delivery features. Due to its intrinsic versatility, BC is the perfect example of a biotechnological response to a clinical problem. In this review, we assess the BC main features and emphasis is given to a specific biomedical application: wound dressings. The production process and the physical-chemical properties that entitle this material to be used as wound dressing namely for burn healing are highlighted. An overview of the most common BC composites and their enhanced properties, in particular physical and biological, is provided, including the different production processes. A particular focus is given to the biochemistry and genetic manipulation of BC. A summary of the current marketed BC-based wound dressing products is presented, and finally, future perspectives for the usage of BC as wound dressing are foreseen.
- Tuning the 1H NMR paramagnetic relaxation enhancement and local order of [Aliquat]+-based systems mixed with DMSOPublication . Cordeiro, Rui; Beira, Maria; Cruz, Carlos; Figueirinhas, João; Corvo, Marta C.; Almeida, Pedro L.; Rosatella, Andreia; Mateus Afonso, Carlos Alberto; Daniel, Carla; Sebastião, PedroUnderstanding the behavior of a chemical compound at a molecular level is fundamental, not only to explain its macroscopic properties, but also to enable the control and optimization of these properties. The present work aims to characterize a set of systems based on the ionic liquids [Aliquat][Cl] and [Aliquat][FeCl4] and on mixtures of these with different concentrations of DMSO by means of H-1 NMR relaxometry, diffusometry and X-ray diffractometry. Without DMSO, the compounds reveal locally ordered domains, which are large enough to induce order fluctuation as a significant relaxation pathway, and present paramagnetic relaxation enhancement for the [Aliquat][Cl] and [Aliquat][FeCl4] mixture. The addition of DMSO provides a way of tuning both the local order of these systems and the relaxation enhancement produced by the tetrachloroferrate anion. Very small DMSO volume concentrations (at least up to 1%) lead to enhanced paramagnetic relaxation without compromising the locally ordered domains. Larger DMSO concentrations gradually destroy these domains and reduce the effect of paramagnetic relaxation, while solvating the ions present in the mixtures. The paramagnetic relaxation was explained as a correlated combination of inner and outer-sphere mechanisms, in line with the size and structure differences between cation and anion. This study presents a robust method of characterizing paramagnetic ionic systems and obtaining a consistent analysis for a large set of samples having different co-solvent concentrations.
- Impedance spectroscopy and electro-optic switching times of a liquid crystal-hydroxypropylcellulose network compositePublication . MANAILA MAXIMEAN, DOINA; Barar, A.; Ganea, C. P.; Almeida, Pedro L.; Danila, OctavianThis paper presents electric and electro-optic studies conducted on a new composite, namely hydroxypropylcellulose network with liquid crystal fillings. The composite was manufactured using the electrospinning method, and deposited on indium tin oxide glass. In terms of electric characterization, the samples were subjected to impedance spectroscopy, their equivalent circuit model was deduced, and the corresponding electric parameters were computed based on the Cole-Cole diagrams and frequency plots of the two impedance components. In terms of electro-optic studies, the optical transmission of the sample under a varying steady-state alternative regime voltage was recorded, and the saturation threshold field was determined. Also, the switching times of the sample with respect to a step signal were determined.