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Simple and effective chitosan based films for the removal of Hg from waters: Equilibrium, kinetic and ionic competition

Publication . Rocha, Luciana S.; Almeida, Ângela; Nunes, Cláudia; Henriques, Bruno; Coimbra, Manuel A.; Lopes, Cláudia B.; Silva, Carlos M.; Duarte, Armando C.; Pereira, Eduarda

The efficiency of chitosan cross-linked with genipin (Chg) and cross-linked with genipin and grafted with caffeic acid (Ch(g+car)) to remove Hg(II) from waters was investigated. An optimal dose of 50 mg L-1 for both chitosan films was selected based on the equilibrium removal percentage and on the contact time required to attain the equilibrium. The sorption extent was dependent on the initial Hg(II) concentration (C-Hg,C-0), with removal efficiencies varying between 79% and 82% for C-Hg,C-0 = 0.05 mg L-1 and between 89% and 94% for C-Hg,C-0 = 0.50 mg L-1. Under ion competition, the Ch(g) and Ch(g+caf) films showed to be effective and selective for mercury in multimetallic solutions containing also cadmium and lead. In the case of natural river and seawaters, the mercury speciation played an important role in the overall sorption process, reducing the percentage removal of Hg. In terms of modeling, the kinetic data were well described by pseudo-first and pseudo-second order models, depending on the experimental conditions. The diffusion models suggested that the entire sorption process of Hg(II) by both Chg and Chg+caf films was essentially controlled by pore diffusion. The equilibrium data were well described by the Sips isotherm, and the estimated capacity was 2.2 and 4.0 mg g(-1) for Chg and Ch(g+caf) films, respectively. In the whole, the results showed that the sorption efficiency was improved by grafting caffeic acid to the polymeric chains of chitosan cross-linked with genipin. (C) 2016 Elsevier B.V. All rights reserved.

2016-09Journal article

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Nutritional potential and toxicological evaluation of tetraselmis sp. CTP4 microalgal biomass produced in industrial photobioreactors

Publication . Pereira, Hugo; Silva, Joana; Santos, Tamara; Gangadhar, Katkam N.; Raposo, Ana; Nunes, Cláudia; Coimbra, Manuel A.; Gouveia, Luísa; Barreira, Luísa; Varela, João

Commercial production of microalgal biomass for food and feed is a recent worldwide trend. Although it is common to publish nutritional data for microalgae grown at the lab-scale, data about industrial strains cultivated in an industrial setting are scarce in the literature. Thus, here we present the nutritional composition and a microbiological and toxicological evaluation of Tetraselmis sp. CTP4 biomass, cultivated in 100-m3 photobioreactors at an industrial production facility (AlgaFarm). This microalga contained high amounts of protein (31.2 g/100 g), dietary fibres (24.6 g/100 g), digestible carbohydrates (18.1 g/100 g) and ashes (15.2 g/100 g), but low lipid content (7.04 g/100 g). The biomass displayed a balanced amount of essential amino acids, n-3 polyunsaturated fatty acids, and starch-like polysaccharides. Significant levels of chlorophyll (3.5 g/100 g), carotenoids (0.61 g/100 g), and vitamins (e.g., 79.2 mg ascorbic acid /100 g) were also found in the biomass. Conversely, pathogenic bacteria, heavy metals, cyanotoxins, mycotoxins, polycyclic aromatic hydrocarbons, and pesticides were absent. The biomass showed moderate antioxidant activity in several in vitro assays. Taken together, as the biomass produced has a balanced biochemical composition of macronutrients and (pro-)vitamins, lacking any toxic contaminants, these results suggest that this strain can be used for nutritional applications.

2019Journal article

Open Access

Catalytic alcoholysis of epoxides using metal-free cucurbituril-based solids

Publication . Bruno, Sofia M.; Gomes, Ana C.; Oliveira, Tânia S. M.; Antunes, Margarida M.; Lopes, Andre D.; Valente, Anabela A.; Gonçalves, Isabel S.; Pillinger, Martyn

Metal-free cucurbit[7]uril (CB7) solid-state assemblies promote acid-catalysed alcoholysis of aliphatic and aromatic epoxides under mild conditions to give beta-alkoxy alcohols, which are important intermediates for the synthesis of a vast range of compounds such as bioactive pharmaceuticals. The catalytic process is heterogeneous and the catalyst can be reused in consecutive runs without any reactivation treatment. The acid species responsible for the catalytic activity of CB7 may be entrapped hydronium ions.

2016Journal article

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Sustainable approach for recycling seafood wastes for the removal of priority hazardous substances (Hg and Cd) from water

Publication . Monteiro, Rui J. R.; Lopes, Cláudia B.; Rocha, Luciana S.; Coelho, João P.; Duarte, Armando C.; Pereira, E.

Mercury and cadmium are considered by the water framework directive priority hazardous substances. In this work, the capacity of crab carapace and clam shell wastes to remove mercury and cadmium from water was evaluated under batch conditions, for realistic contamination scenarios in monometallic and binary solutions. The results evidenced that in monometallic solutions and under studied operational conditions, both biosorbents can achieve Hg2+ removal efficiencies higher than 80% and the kinetic process is well described by two of the most widely used equations, the pseudo-second order and the Elovich model. In terms of biosorption equilibrium, crab carapace and clam shell wastes displayed very distinct behaviours. While clam shells achieve the complete monolayer coverage and the isotherm is well described by the Langmuir model, crab carapace powder display a more unusual behaviour, that is well described by the BET isotherm, and is characterized by an almost convex shape to the concentration axis, with an infinite slope for an Hg2+ concentration in solution around 25 mu g/L. In binary solutions, both wastes are able to uptake simultaneously Hg2+ and Cd2+, however the uptake of Hg2+ was inhibited in some extent, attributed to the high kinetic and equilibrium selectivities of the bio-wastes for cadmium. (C) 2016 Elsevier Ltd. All rights reserved.

2016-07Journal article

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Solid-state study of the structure and host-guest chemistry of cucurbituril-ferrocene inclusion complexes

Publication . Gomes, Ana C.; Magalhães, Clara I. R.; Oliveira, Tânia S. M.; Lopes, Andre D.; Gonçalves, Isabel S.; Pillinger, Martyn

Inclusion complexes of ferrocene (Fc) with cucurbit[n]urils (n = 7, 8) have been prepared via a rapid microwave-assisted hydrothermal approach. Solids were isolated and characterised by elemental analysis, powder X-ray diffraction (PXRD), spectroscopic, and thermoanalytical methods. The UV-Vis spectra support the presence of Fc in Fc@CB7 and a mixture of Fc and ferrocenium ions in Fc@CB8. Partial oxidation of Fc to Fc(+) takes place in situ mainly due to the presence of acid of crystallisation in CB8. On the basis of PXRD, the complex Fc@CB8 is classified into an isostructural series that is formed by several CB8-containing compounds that crystallise in the space group /4(1)/a and have similar unit cell dimensions and CB8 packing motifs. The FT-IR and Raman spectra of Fc@CB7 are compared with those of the CB7 host and the Fc guest starting materials, revealing significant frequency shifts of some Fc-centered vibrational modes upon complexation. Blueshifts of the Fe-Cp stretching and ring tilt bands are attributed to encapsulation of Fc monomers in a constrained environment, leading to restricted motion effects and/or a change in the Fc conformation from staggered to eclipsed. The absence of comparable shifts for Fc@CB8 point to a weaker host-guest interaction as a consequence of the larger cavity size. The different host-guest interactions are also evident through a comparison of the C-13{H-1} CP MAS NMR spectra. Thermogravimetric analysis for the inclusion compounds reveals that sublimation of Fc is inhibited by molecular encapsulation to the extent that oxidative decomposition of the organoiron species takes place concurrently with cucurbituril decomposition, leading to the formation of hematite, alpha-Fe2O3.

2016Journal article

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