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2018
Kumar, K, Correia M, Pires VR, Dhillon A, Sharma K, Rajulapati V, Fontes CMGA, Carvalho AL, Goyal A.  2018.  Novel insights into the degradation of β-1,3-glucans by the cellulosome of Clostridium thermocellum revealed by structure and function studies of a family 81 glycoside hydrolase. International Journal of Biological Macromolecules. :-. AbstractWebsite

Abstract The family 81 glycoside hydrolase (GH81) from Clostridium thermocellum is a β-1,3-glucanase belonging to cellulosomal complex. The gene encoding \{GH81\} from Clostridium thermocellum (CtLam81A) was cloned and expressed displaying a molecular mass of  82 kDa. CtLam81A showed maximum activity against laminarin (100 U/mg), followed by curdlan (65 U/mg), at pH 7.0 and 75 °C. CtLam81A displayed Km, 2.1 ± 0.12 mg/ml and Vmax, 109 ± 1.8 U/mg, against laminarin under optimized conditions. CtLam81A activity was significantly enhanced by Ca2+ or Mg2+ ions. Melting curve analysis of CtLam81A showed an increase in melting temperature from 91 °C to 96 °C by Ca2+ or Mg2+ ions and decreased to 82 °C by EDTA, indicating that Ca2+ and Mg2+ ions may be involved in catalysis and in maintaining structural integrity. \{TLC\} and MALDI-TOF analysis of β-1,3-glucan hydrolysed products released initially, showed β-1,3-glucan-oligosaccharides degree of polymerization (DP) from \{DP2\} to DP7, confirming an endo-mode of action. The catalytically inactive mutant CtLam81A-E515A generated by site-directed mutagenesis was co-crystallized and tetragonal crystals diffracting up to 1.4 Å resolution were obtained. CtLam81A-E515A contained 15 α-helices and 38 β-strands forming a four-domain structure viz. a β-sandwich domain I at N-terminal, an α/β-domain II, an (α/α)6 barrel domain III, and a small 5-stranded β-sandwich domain IV.

Tufa, RA, Pawlowski S, Veerman J, Bouzek K, Fontananova E, di Profio G, Velizarov S, Goulão Crespo J, Nijmeijer K, Curcio E.  2018.  Progress and prospects in reverse electrodialysis for salinity gradient energy conversion and storage. Applied Energy. 225:290-331. AbstractWebsite

Salinity gradient energy is currently attracting growing attention among the scientific community as a renewable energy source. In particular, Reverse Electrodialysis (RED) is emerging as one of the most promising membrane-based technologies for renewable energy generation by mixing two solutions of different salinity. This work presents a critical review of the most significant achievements in RED, focusing on membrane development, stack design, fluid dynamics, process optimization, fouling and potential applications. Although RED technology is mainly investigated for energy generation from river water/seawater, the opportunities for the use of concentrated brine are considered as well, driven by benefits in terms of higher power density and mitigation of adverse environmental effects related to brine disposal. Interesting extensions of the applicability of RED for sustainable production of water and hydrogen when complemented by reverse osmosis, membrane distillation, bio-electrochemical systems and water electrolysis technologies are also discussed, along with the possibility to use it as an energy storage device. The main hurdles to market implementation, predominantly related to unavailability of high performance, stable and low-cost membrane materials, are outlined. A techno-economic analysis based on the available literature data is also performed and critical research directions to facilitate commercialization of RED are identified.

2017
Bernardo, MMS, Madeira CAC, dos Santos Nunes NCL, Dias DACM, Godinho DMB, de Jesus Pinto MF, do Nascimento Matos IAM, Carvalho APB, de Figueiredo Ligeiro Fonseca IM.  2017.  Study of the removal mechanism of aquatic emergent pollutants by new bio-based chars, Oct. Environmental Science and Pollution Research. 24:22698–22708., Number 28 AbstractWebsite

This work is dedicated to study the potential application of char byproducts obtained in the gasification of rice husk (RG char) and rice husk blended with corn cob (RCG char) as removal agents of two emergent aquatic contaminants: tetracycline and caffeine. The chars presented high ash contents (59.5–81.5{%}), being their mineral content mainly composed of silicon (as silica) and potassium. The samples presented a strong basic character, which was related to its higher mineral oxides content. RCG char presented better textural properties with a higher apparent surface area (144 m2 g−1) and higher micropore content (V micro = 0.05 cm3 g−1). The alkaline character of both chars promoted high ecotoxicity levels on their aqueous eluates; however, the ecotoxic behaviour was eliminated after pH correction. Adsorption experiments showed that RG char presented higher uptake capacity for both tetracycline (12.9 mg g−1) and caffeine (8.0 mg g−1), indicating that textural properties did not play a major role in the adsorption process. For tetracycline, the underlying adsorption mechanism was complexation or ion exchange reactions with the mineral elements of chars. The higher affinity of RG char to caffeine was associated with the higher alkaline character presented by this char.

Kryshtafovych, A, Albrecht R, Baslé A, Bule P, Caputo AT, Carvalho AL, Chao KL, Diskin R, Fidelis K, Fontes CMGA, Fredslund F, Gilbert HJ, Goulding CW, Hartmann MD, Hayes CS, Herzberg O, Hill JC, Joachimiak A, Kohring G-W, Koning RI, {Lo Leggio} L, Mangiagalli M, Michalska K, Moult J, Najmudin S, Nardini M, Nardone V, Ndeh D, Nguyen TH, Pintacuda G, Postel S, van Raaij MJ, Roversi P, Shimon A, Singh AK, Sundberg EJ, Tars K, Zitzmann N, Schwede T.  2017.  Target highlights from the first post-PSI CASP experiment (CASP12, May-August 2016), oct. Proteins: Structure, Function, and Bioinformatics. AbstractWebsite

The functional and biological significance of the selected CASP12 targets are described by the authors of the structures. The crystallographers discuss the most interesting structural features of the target proteins and assess whether these features were correctly reproduced in the predictions submitted to the CASP12 experiment. This article is protected by copyright. All rights reserved.

Carlos, {FF}, Veigas B, Matias {AS }, c}alo Dória G{\c, Flores O, Baptista {PV}.  2017.  Allele specific LAMP- gold nanoparticle for characterization of single nucleotide polymorphisms, dec. Biotechnology Reports. 16:21–25.: Springer Science Business Media Abstract

Due to their relevance as disease biomarkers and for diagnostics, screening of single nucleotide polymorphism (SNPs) requires simple and straightforward strategies capable to provide results in medium throughput settings. Suitable approaches relying on isothermal amplification techniques have been evolving to substitute the cumbersome and highly specialized PCR amplification detection schemes. Nonetheless, identification of an individual's genotype still requires sophisticated equipment and laborious methods. Here, we present a low-cost and reliable approach based on the allele specific loop-mediated isothermal amplification (AS-LAMP) coupled to ssDNA functionalized gold nanoparticle (Au-nanoprobe) colorimetric sequence discrimination. The Au-nanoprobe integration allows for the colorimetric detection of AS-LAMP amplification product that can be easily interpreted in less than 15 min. We targeted a clinical relevant SNP responsible for lactose intolerance (-13910C/T dbSNP rs#: 4988235) to demonstrate its proof of concept and full potential of this novel approach.

Gouveia, J.P., Dias L, Seixas J, Simões S.  2017.  INSMART – Integrative Energy Planning For Cities Low Carbon Futures: Analytical Framework, 8th February. 3rd Energy for Sustainability Conference. , Funchal, Portugal
Dias, L., Simões S, Gouveia JP, Seixas J.  2017.  Integrative Energy Planning For Cities Low Carbon Futures: Modelling and Scenarios results, 8th February. 3rd Energy for Sustainability Conference. , Funchal, Portugal
Sulim, O, Ribeiro R, Esteves I, Antunes C, Garate A, Duarte P, Ferreira I, Mota J, Plaza M.  2017.  Design of structured adsorbents for aplications in gas adsorption processes - Conventional shaping vs 3D-Printed formulation, 5-10 March. Abstract

Microporous materials highly activated and with potential to be used as adsorbents in many applications for gas
separation/purification are usually available as powders. These solids usually have a great and reversible gas
uptake, high gas selectivity, good chemical and thermal stability, but are unsuitable to be used in gas adsorption
processes, such as Pressure Swing Adsorption (PSA) or Simulated Moving Bed (SMB).
Zeolites, carbons and more recently metal-organic frameworks (MOFs) are examples of those materials. Their
use in adsorption-based processes are dependent of their upgrading from powders (micrometer scale) to
particles (pellets, spheres or granules at millimeter scale). This would overcome large pressure drops and
consequent energy consumptions when packing adsorbent columns in those processes. Thus, shaping
adsorbents is an important step to use them in industry, although it greatly affects their capacity and selectivity
towards a specific gas separation.
In this work, we explore techniques to shape powdered adsorbents, followed by their textural and mechanical
characterizations, and the study of their adsorption properties towards the main components of post-combustion
flues gases (CO2 and N2). Materials densification is proposed by employing two approaches:
- Conventional shaping through binderless mechanical compression and binder-containing extrusion; and
- Formulation by 3D printing (or additive manufacturing) to produce packed bed morphologies that
precisely replicate computer aided design (CAD) models.
Porous separation media are important for fluid-solid contacting in many unit operations, including adsorption.
Due to practical limitations, media particles are typically packed randomly into a column in a shaped form,
allowing fluid to flow through the interstitial voids. Key to the effectiveness of packed columns are the flowrelated properties of mass transfer, fluid distribution and dispersion, and back pressure, which in turn depend
upon packing geometry. Until now, no alternative was found to overcome this limitation and have optimal
ordered packing arrangements at the micron scale. 3D-Printing (or additive manufacturing) brings a wide range
of benefits that traditional methods of manufacturing or prototyping simply cannot. With this approach, complex
ordered geometries, that are not possible by conventional extrusion, can be designed and printed for a porous
media, being the equipment resolution the only limiting step to overcome.
The effect of parameters like compression force, particle sieving, binder nature, binder/adsorbent ratio were
firstly studied using conventional shaping techniques, as a basis for the consequent development of 3D-printed
formulations. The structured samples are then characterized and adsorption equilibria studies are performed on
them to evaluate their performance as media for gas adsorption separation processes. A volumetric/manometric
adsorption unit built in-house was used for this purpose. Relevant experimental data is obtained, which allows to
conclude that 3D-printed media can be an alternative porous media for application in gas adsorption processes.

Mendoza, J, Basilio N, Dangles O, Mora N, Al Bittar S, Pina F.  2017.  Binding of the five multistate species of the anthocyanin analog 7-beta-D-glucopyranosyloxy-4'-hydroxyflavylium to the beta-cyclodextrin derivative captisol, 2017. Dyes and Pigments. 143:479-487. AbstractWebsite
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Huang, RJ, Avo J, Northey T, Chaning-Pearce E, dos Santos PL, Ward JS, Data P, Etherington MK, Fox MA, Penfold TJ, Berberan-Santos MN, Lima JC, Bryce MR, Dias FB.  2017.  The contributions of molecular vibrations and higher triplet levels to the intersystem crossing mechanism in metal-free organic emitters, 2017. Journal of Materials Chemistry C. 5(25):6269-6280. AbstractWebsite
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Delgado, JM, Nunes D, Fortunato E, Laia CAT, Branco LC, Vilarigues M.  2017.  The effect of three luminescent ionic liquids on corroded glass surfaces - A first step into stained-glass cleaning, 2017. Corrosion Science. 118:109-117. AbstractWebsite
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Delgado, JM, Nunes D, Fortunato E, Laia CAT, Branco LC, Vilarigues M.  2017.  The effect of three luminescent ionic liquids on corroded glass surfaces – A first step into stained-glass cleaning, 2017. Corrosion Science. 118:109-117. AbstractWebsite
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Martins, ICB, Oliveira MC, Diogo HP, Branco LC, Duarte MT.  2017.  MechanoAPI-ILs: Pharmaceutical Ionic Liquids Obtained through Mechanochemical Synthesis, 2017. Chemsuschem. 10(7):1360-1363. AbstractWebsite
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Santoro, S, Vidorreta IM, Sebastian V, Moro A, Coelhoso IM, Portugal CAM, Lima JC, Desiderio G, Lombardo G, Drioli E, Mallada R, Crespo JG, Criscuoli A, Figoli A.  2017.  A non-invasive optical method for mapping temperature polarization in direct contact membrane distillation, 2017. Journal of Membrane Science. 536:156-166. AbstractWebsite
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Romero, MA, Basilio N, Moro AJ, Domingues M, Gonzalez-Delgado JA, Arteaga JF, Pischel U.  2017.  Photocaged Competitor Guests: A General Approach Toward Light-Activated Cargo Release From Cucurbiturils, 2017. Chemistry-a European Journal. 23(53):13105-13111. AbstractWebsite
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Silveira, CM, Castro MA, Dantas JM, Salgueiro C, Murgida DH, Todorovic S.  2017.  Structure, electrocatalysis and dynamics of immobilized cytochrome PccH and its microperoxidase, 2017. Physical Chemistry Chemical Physics. 19(13):8908-8918.: The Royal Society of Chemistry AbstractWebsite

Geobacter sulfurreducens cells have the ability to exchange electrons with conductive materials, and the periplasmic cytochrome PccH plays an essential role in the direct electrode-to-cell electron transfer in this bacterium. It has atypically low redox potential and unique structural features that differ from those observed in other c-type cytochromes. We report surface enhanced resonance Raman spectroscopic and electrochemical characterization of the immobilized PccH, together with molecular dynamics simulations that allow for the rationalization of experimental observations. Upon attachment to electrodes functionalized with partially or fully hydrophobic self-assembled monolayers, PccH displays a distribution of native and non-native heme spin configurations, similar to those observed in horse heart cytochrome c. The native structural and thermodynamic features of PccH are preserved upon attachment mixed hydrophobic (-CH3/-NH2) surfaces, while pure -OH, -NH2 and -COOH surfaces do not provide suitable platforms for its adsorption, indicating that its still unknown physiological redox partner might be membrane integrated. Neither of the employed immobilization strategies results in electrocatalytically active PccH capable of the reduction of hydrogen peroxide. Pseudoperoxidase activity is observed in immobilized microperoxidase, which is enzymatically produced from PccH and spectroscopically characterized. Further improvement of PccH microperoxidase stability is required for its application in electrochemical biosensing of hydrogen peroxide.

Sousa, JR, Silveira CM, Fontes P, Roma-Rodrigues C, Fernandes AR, Van Driessche G, Devreese B, Moura I, Moura JJG, Almeida GM.  2017.  Understanding the response of Desulfovibrio desulfuricans ATCC 27774 to the electron acceptors nitrate and sulfate - biosynthetic costs modulate substrate selection, 2017. 1865(11, Part A):1455-1469. AbstractWebsite
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Beira, MJ, Daniel CI, Almeida PL, Corvo MC, Rosatella AA, Afonso CAM, Sebastiao PJ.  2017.  1H NMR Relaxometry and Diffusometry Study of Magnetic and Non-Magnetic Ionic Liquid-Based Solutions: Co-Solvent and Temperature Effects. The Journal of Physical Chemistry B. : ACS Publications AbstractWebsite

In this work, 1H NMR relaxometry and diffusometry as well as viscometry experiments were carried out as a means to study the molecular dynamics of magnetic and non-magnetic ionic liquid-based systems. In order to evaluate the effect of a co-solvent on the super-paramagnetic properties observed for Aliquat-iron-based magnetic ionic liquids, mixtures comprising different concentrations, 1% and 10% (v/v), of DMSO-d6 were prepared and analyzed. The results suggest that, when at low concentrations, DMSO-d6 promotes more structured ionic arrangements, thus enhancing these super-paramagnetic properties. Furthermore, the analysis of temperature and water concentration effects allowed to conclude that neither one of these variables sufficiently affected the super-paramagnetic properties of the studied magnetic ionic liquids.

Marques, AC, Santos L, Dantas JM, Gonçalves A, Casaleiro S, Martins R, Salgueiro CA, Fortunato E.  2017.  Advances in electrochemically active bacteria: Physiology and ecology. Handbook of Online and Near-real-time Methods in Microbiology. : CRC Press Abstract

The discovery of microorganisms with the ability of Extracellular Electron Transfer (EET), nearly three decades ago, sparked interest due to their ability to be used in diverse applications that can range from bioremediation to electricity production in Microbial Fuel Cells (MFC). Microbial respiration is based on electron transfer from a donor to an electron acceptor, through a series of stepwise electron transfer events that generate the necessary metabolic energy. Some microorganisms, such as Pseudomonas species, Shewanella putrefaciens or Geothrix fermentans are able to produce electrochemical mediators to increase the EET. The mechanical stability of the biofilm is provided by the biofilm matrix, a hydrated extracellular polymeric matrix that encases the biofilm cells. The biofilm matrix could potentially offer a resistance pathway to EET unless bacteria develop strategies to increase its conductivity. MFC devices currently being used and studied do not generate sufficient power to support widespread and cost-effective applications.

Dupont, J, Simon NM, Zanatta M, dos Santos FP, Corvo MC, Cabrita EJ.  2017.  Carbon dioxide capture by aqueous ionic liquid solutions. ChemSusChem. AbstractWebsite

Confined water in aqueous solutions of imidazolium-based ionic liquids (ILs) associated with acetate and imidazolate anions react reversibly with CO2 to yield bicarbonate. Three types of CO2 sorption in these “IL aqueous solutions” were observed: physical, CO2-imidazolium adduct generation, and bicarbonate formation (up to 1.9 molbicarbonate mol−1 of IL), resulting in a 10:1 (molar ratio) total absorption of CO2 relative to imidazolate anions in the presence of water 1:1000 (IL/water). These sorption values are higher than the classical alkanol amines or even alkaline aqueous solutions under similar experimental conditions.

Cruz, H, Jordão N, Amorim P, Dionísio M, Branco LC.  2017.  Deep Eutectic Solvents as Suitable Electrolytes for Electrochromic Devices. ACS Sustainable Chemistry and Engineering. 6(2):2240-2249.Website
Almeida, RM, Dell'Acqua S, Moura I, Pauleta SR, Moura JJG.  2017.  Electron transfer and molecular recognition in denitrification and nitrate dissimilatory pathways. Metalloenzymes in Denitrification: Applications and Environmental Impacts, RSC Metallobiology Series No. 9 (ISBN: 978-1-78262-376-2).. (Moura, I., Moura, J. J. G., Pauleta, S. R., Maia, L. B., Eds.).:252-286.: Royal Society of Chemistry
Delgado-Lima, A, Borges JP, Ferreira I, Machado A.  2017.  Fluorescent and conductive cellulose acetate-based membranes with porphyrins. Materials today Communications. 11:26-37. AbstractWebsite

The unique properties of electrospun nanofibers combined with functional compounds allow the preparation of novelty materials that can be employed in a wide range of applications. Among a vast number of polymers, Cellulose Acetate (CA) it is considered easy to electrospun and it was employed as the polymeric matrix, where free and iridium-porphyrins were incorporated. Two different solvent systems were employed according to the porphyrin used, and the best dispersion level on both the electrospun solution and the membranes, was achieved with the iridium porphyrin. The nanofibers with this porphyrin also exhibited electrical properties, while the fluorescence was quenched by the presence of specific axial ligands.

Delgado-Lima, A, Borges JP, Ferreira IM, Machado AV.  2017.  Fluorescent and conductive cellulose acetate-based membranes with porphyrins. Materials Today Communications. 11:26-37. AbstractWebsite

The unique properties of electrospun nanofibers combined with functional compounds allow the preparation of novelty materials that can be employed in a wide range of applications. Among a vast number of polymers, Cellulose Acetate (CA) it is considered easy to electrospun and it was employed as the polymeric matrix, where free and iridium-porphyrins were incorporated. Two different solvent systems were employed according to the porphyrin used, and the best dispersion level on both the electrospun solution and the membranes, was achieved with the iridium porphyrin. The nanofibers with this porphyrin also exhibited electrical properties, while the fluorescence was quenched by the presence of specific axial ligands.

Dias, AMGC, Roque ACA.  2017.  The future of protein scaffolds as affinity reagents for purification. Biotechnology and Bioengineering. 114:481–491., Number 3 Abstract

Affinity purification is one of the most powerful separation techniques extensively employed both at laboratory and production scales. While antibodies still represent the gold standard affinity reagents, others derived from non-immunoglobulin scaffolds emerged as interesting alternatives in particular for affinity purification. The lower costs of production, fast ligand development and high robustness are appealing advantages of non-immunoglobulin scaffolds. These have successfully been used in the affinity purification of relevant targets as antibodies, human serum albumin, transferrin and other biomarkers, as reviewed in this work. Furthermore, a critical assessment on the strengths, weaknesses, opportunities and threats related with the implementation of non-immunoglobulin scaffolds as ligands in affinity purification are discussed. This article is protected by copyright. All rights reserved.