Contreras, J, Martins R, Wojcik P, Filonovich S, Águas H, Gomes L, Fortunato E, Ferreira I.
2014.
Color sensing ability of an amorphous silicon position sensitive detector array system. Sensor Actuat. A-Phys.. 205:26-37.
AbstractThe color sensing ability of a data acquisition prototype system integrating a 32 linear array of 1D amorphous silicon position sensitive detectors (PSD) was analyzed. Besides being used to reproduce a 3D profile of highly reflective surfaces, here we show that it can also differentiate primary red, green, blue (RGB) and derived colors. This was realized by using an incident beam with a RGB color combination and adequate integration times taking into account that a color surface mostly reflects its corresponding color. A mean colorimetric error of 25.7 was obtained. Overall, we show that color detection is possible via the use of this sensor array system, composed by a simpler amorphous silicon pin junction.
Marcelo, F, Garcia-Martin F, Matsushita T, Sardinha J, Coelho H, Oude-Vrielink A, Koller C, André S, Cabrita EJ, Gabius H-J, Nishimura S-I, Jiménez-Barbero J, Cañada JF.
2014.
Delineating binding modes of Gal/GalNAc and structural elements of the molecular recognition of tumor-associated mucin glycopeptides by the human macrophage galactose-type lectin.. Chem. Eur. J.. 20:16147-16155.
AbstractThe human macrophage galactose-type lectin (MGL) is a key physiological receptor for the carcinoma-associated Tn antigen (GalNAc-α-1-O-Ser/Thr) in mucins. NMR and modeling-based data on the molecular recognition features of synthetic Tn-bearing glycopeptides by MGL are presented. Cognate epitopes on the sugar and matching key amino acids involved in the interaction were identified by saturation transfer difference (STD) NMR spectroscopy. Only the amino acids close to the glycosylation site in the peptides are involved in lectin contact. Moreover, control experiments with non-glycosylated MUC1 peptides unequivocally showed that the sugar residue is essential for MGL binding, as is Ca(2+) . NMR data were complemented with molecular dynamics simulations and Corcema-ST to establish a 3D view on the molecular recognition process between Gal, GalNAc, and the Tn-presenting glycopeptides and MGL. Gal and GalNAc have a dual binding mode with opposite trend of the main interaction pattern and the differences in affinity can be explained by additional hydrogen bonds and CH-π contacts involving exclusively the NHAc moiety.
Madariaga, D, Martínez-Sáez N, Somovilla VJ, Coelho H, González JV, Castro-López J, Asensio JL, Jimenez-Barbero J, Busto JH, Avenoza A, Marcelo F, Hurtado-Guerrero R, Corzana F, Peregrina JM.
2014.
Detection of Tumor-Associated Glycopeptides by Lectins: the Peptide Context Modulates Carbohydrate Recognition. ACS Chem. Biol.. 10:747-56.
AbstractTn antigen (α-O-GalNAc-Ser/Thr) is a convenient cancer biomarker that is recognized by antibodies and lectins. This work yields remarkable results for two plant lectins in terms of epitope recognition and reveals that these receptors show higher affinity for Tn antigen when it is incorporated in the Pro-Asp-Thr-Arg (PDTR) peptide region of mucin MUC1. In contrast, a significant affinity loss is observed when Tn antigen is located in the Ala-His-Gly-Val-Thr-Ser-Ala (AHGVTSA) or Ala-Pro-Gly-Ser-Thr-Ala-Pro (APGSTAP) fragments. Our data indicate that the charged residues, Arg and Asp, present in the PDTR sequence establish noteworthy fundamental interactions with the lectin surface as well as fix the conformation of the peptide backbone, favoring the presentation of the sugar moiety toward the lectin. These results may help to better understand glycopeptide-lectin interactions and may contribute to engineer new binding sites, allowing novel glycosensors for Tn antigen detection to be designed
Rueff, A-S, Chastanet A, Dominguez-Escobar J, Yao Z, Yates J, Prejean M-V, Delumeau O, P. Noirot, Wedlich-Soldner R, Filipe SR, Carballido-Lopez R.
2014.
An early cytoplasmic step of peptidoglycan synthesis is associated to MreB in Bacillus subtilis. Mol. Microbiol. 91:348-362.
Soares, PIP, Alves A, Pereira L, Coutinho J, Ferreira I, Novo C, Borges JP.
2014.
Effects of surfactants on the magnetic properties of iron oxide colloids. Journal of Colloid and Interface Science. 419:46–51.
AbstractIron oxide nanoparticles are having been extensively investigated for several biomedical applications such as hyperthermia and magnetic resonance imaging. However, one of the biggest problems of these nanoparticles is their aggregation.
Taking this into account, in this study the influence of three different surfactants (oleic acid, sodium citrate and Triton X-100) each one with various concentrations in the colloidal solutions stability was analyzed by using a rapid and facile method, the variation in the optical absorbance along time.
The synthesized nanoparticles through chemical precipitation showed an average size of 9 nm and a narrow size distribution. X-ray diffraction pattern and Fourier Transform Infrared analysis confirmed the presence of pure magnetite. SQUID measurements showed superparamagnetic properties with a blocking temperature around 155 K. In addition it was observed that neither sodium citrate nor Triton X-100 influences the magnetic properties of the nanoparticles. On the other hand, oleic acid in a concentration of 64 mM decreases the saturation magnetization from 67 to 45 emu/g. Oleic acid exhibits a good performance as stabilizer of the iron oxide nanoparticles in an aqueous solution for 24 h, for concentrations that lead to the formation of the double layer.
Soares, PIP, Alves AMR, Pereira LCJ, Coutinho JT, Ferreira IMM, Novo CMM, Borges JPMR.
2014.
Effects of surfactants on the magnetic properties of iron oxide colloids. J. Colloid Interface Sci.. 419:46-51.
AbstractIron oxide nanoparticles are having been extensively investigated for several biomedical applications such as hyperthermia and magnetic resonance imaging. However, one of the biggest problems of these nanoparticles is their aggregation.
Taking this into account, in this study the influence of three different surfactants (oleic acid, sodium citrate and Triton X-100) each one with various concentrations in the colloidal solutions stability was analyzed by using a rapid and facile method, the variation in the optical absorbance along time.
The synthesized nanoparticles through chemical precipitation showed an average size of 9 nm and a narrow size distribution. X-ray diffraction pattern and Fourier Transform Infrared analysis confirmed the presence of pure magnetite. SQUID measurements showed superparamagnetic properties with a blocking temperature around 155 K. In addition it was observed that neither sodium citrate nor Triton X-100 influences the magnetic properties of the nanoparticles. On the other hand, oleic acid in a concentration of 64 mM decreases the saturation magnetization from 67 to 45 emu/g. Oleic acid exhibits a good performance as stabilizer of the iron oxide nanoparticles in an aqueous solution for 24 h, for concentrations that lead to the formation of the double layer.
Silva, M, Figueiredo AM, Cabrita EJ.
2014.
Epitope mapping of imidazolium cation in ionic liquid-protein interactions unveils the balance between hydrophobicity and electrostatics towards protein destabilisation. Physical Chemistry Chemical Physics. in press
AbstractWe investigated imidazolium-based ionic liquid (IL) interactions with human serum albumin (HSA) to discern the level of cation interactions towards protein stability. STD-NMR spectroscopy was used to observe the imidazolium ILs protons involved in direct binding and to identify the interactions responsible for changes in Tm as accessed by differential scanning calorimetry (DSC). Cations influence protein stability less than anions but still significantly. It was found that longer alkyl side chains of imidazolium-based ILs (more hydrophobic) are associated with a higher destabilisation effect on HSA than short-alkyl groups (less hydrophobic). The reason for such destabilisation lies on the increase surface contact area of the cation with the protein, particularly on the hydrophobic contacts promoted by the terminus of the alkyl chain. The relevance of the hydrophobic contacts is clearly demonstrated by the introduction of a polar moiety in the alkyl chain: a methoxy or alcohol group. Such structural modification reduces the degree of hydrophobic contacts with HSA explaining the lesser extent of protein destabilisation when compared to longer alkyl side chain groups: above [C2mim]+. Competition STD-NMR experiments using [C2mim]+, [C4mim]+ and [C2OHmim]+ also validate the importance of the hydrophobic interactions. The combined effect of cation and anion interactions was explored using 35Cl NMR. Such experiments show that the nature of the cation has no influence in the anion-protein contacts, still the nature of the anion modulates the cation-protein interaction. Herein we propose that more destabilising anions are likely to be a result of a partial contribution from the cation as a direct consequence of the different levels of interaction (cation-anion pair and cation-protein).
C, N, R. F, M.P.F. G, M. E, B.A. S, R.C.C. M, L. R, T. M.
2014.
Eu3+ luminescence in aluminophosphate glasses. Journal of Luminescence. 145:582-587.
AbstractWith a 4f6 electronic configuration, europium ions in the trivalent charge state are known to be efficient activators in wide band gap matrices. Embedded in the aluminophosphate (Li2O–BaO–Al2O3–La2O3–P2O5) glasses the optically activated Eu3+ ions lead to intense room temperature orange/red luminescence with 16–23 Cd/m2 by using ultraviolet pumping. The as-prepared and heat treated europium doped glasses for temperatures below and above Tg were studied by room temperature Raman spectroscopy, absorption, photoluminescence excitation, temperature dependent and time dependent photoluminescence. When the samples are excited by 325 nm wavelength photons, an enhancement of the red luminescence intensity by ca. one order of magnitude was found to occur for temperatures between 14 K and 350 K, for all the doped glasses. On the other hand, by using resonant excitation on the 5L6 Eu3+ excited state (λexc~390 nm) the ion emission intensity was found to be nearly constant for temperatures up to 500 K. For higher temperatures a steeper decrease of the luminescence intensity occurs due to non-radiative competitive channels described by activation energies of ca. 235 meV and 450 meV by using 325 and 390 nm wavelength photons as excitation, respectively. The lifetime of the 5D0 level in these glasses is ca. 2.93 ms. A discussion of the thermal population and de-excitation mechanisms is performed.
Zubizarreta, C., Berasategui, E. G., Bayón, R., Escobar Galindo, R., Barros, R., Gaspar, Diana, Nunes, D., Calmeiro, T., Martins, Fortunato, Barriga J.
2014.
Evaluation of the optoelectronic properties and corrosion behavior of Al2O3-doped ZnO films prepared by dc pulsed magnetron sputtering. Journal of Physics D: Applied Physics. 47:13pp.
Dantas, JM, Morgado L, Catarino T, Kokhan O, Pokkuluri PR, Salgueiro CA.
2014.
Evidence for interaction between the triheme cytochrome PpcA from Geobacter sulfurreducens and anthrahydroquinone-2,6-disulfonate, an analog of the redox active components of humic substances. Biochim Biophys Acta. 1837(6):750-760.
AbstractThe bacterium Geobacter sulfurreducens displays an extraordinary respiratory versatility underpinning the diversity of electron donors and acceptors that can be used to sustain anaerobic growth. Remarkably, G. sulfurreducens can also use as electron donors the reduced forms of some acceptors, such as the humic substance analog anthraquinone-2,6-disulfonate (AQDS), a feature that confers environmentally competitive advantages to the organism. Using UV-visible and stopped-flow kinetic measurements we demonstrate that there is electron exchange between the triheme cytochrome PpcA from Gs and AQDS. 2D-(1)H-(15)N HSQC NMR spectra were recorded for (15)N-enriched PpcA samples, in the absence and presence of AQDS. Chemical shift perturbation measurements, at increasing concentration of AQDS, were used to probe the interaction region and to measure the binding affinity of the PpcA-AQDS complex. The perturbations on the NMR signals corresponding to the PpcA backbone NH and heme substituents showed that the region around heme IV interacts with AQDS through the formation of a complex with a definite life time in the NMR time scale. The comparison of the NMR data obtained for PpcA in the presence and absence of AQDS showed that the interaction is reversible. Overall, this study provides for the first time a clear illustration of the formation of an electron transfer complex between AQDS and a G. sulfurreducens triheme cytochrome, shedding light on the electron transfer pathways underlying the microbial oxidation of humics.
Sequeira, SO, Cabrita EJ, Macedo MF.
2014.
Fungal Biodeterioration of Paper: How are Paper and Book Conservators Dealing with it? An International Survey Restaurator. International Journal for the Preservation of Library and Archival Material. 35(2):181–199.
AbstractPaper biodeterioration by fungi has always been a concern in archives, libraries and museums. Several guidelines have been published regarding the prevention of fungal development in paper collections and recovery of affected objects, but what is actually being implemented from the literature by worldwide paper and book conservators? How common is this type of biodeterioration? What needs to be further studied? In order to access this information we conducted an online international questionnaire with participants from 20 different countries. The results show that fungal biodeterioration is highly common in paper collections. All of the respondents already had to deal with paper deteriorated by fungi, and although the vast majority uses active measures to prevent fungal development, most of them have already experienced active fungal infestations. The mainly used preventive measures are the ones concerned with the control of the environmental conditions in storage and display rooms. Drying the affected paper objects and applying 70% ethanol are the most preferred options to stop active fungal growth. The study of non-toxic and safer antifungals is considered here as the most relevant research topic in the area of paper biodeterioration by fungi, meaning that the options currently available are not totally satisfactory.
Conde, J, Larguinho M, Cordeiro A, Raposo LR, Costa PM, Santos S, Diniz MS, Fernandes AR, Baptista PV.
2014.
Gold-nanobeacons for gene therapy: evaluation of genotoxicity, cell toxicity and proteome profiling analysis. Nanotoxicology. 8(5):521-32.
Barroso, T, Casimiro T, Ferraria A, Mattioli F, Aguiar-Ricardo A, Roque ACA.
2014.
Hybrid monoliths for magnetically-driven protein separations. Adv. Funct. Mater.. 24(28):4528–4541.
AbstractMonoliths represent powerful platforms for isolation of large molecules with high added value. This work presents a hybrid approach for antibody (Ab) capture and release. Using mostly natural polymers and clean processes, it is possible to create macroporous monoliths with well-defined porous networks, tuneable mechanical properties, and easy functionalization with a biomimetic ligand specific for Ab. Magnetic nanoparticles (MNPs) are embedded on the monolith network to confer a controlled magnetic response that facilitates and accelerates Ab recovery in the elution step. The hybrid monolithic systems prepared with agarose or chitosan/poly(vinyl alcohol) (PVA) blends exhibit promising binding capacities of Abs directly from cell-culture extracts (120 ± 10 mg Ab g−1 support) and controlled Ab magnetically-assisted elution yielding 95 ± 2% recovery. Moreover, a selective capture of mAbs directly from cell culture extracts is achieved yielding a final mAb preparation with 96% of purity.
Carvalho, T, Augusto V, Rocha A, Lourenco NMT, Correia NT, Barreiros S, Vidinha P, Cabrita EJ, Dionisio M.
2014.
Ion Jelly Conductive Properties Using Dicyanamide-Based Ionic Liquids. Journal of Physical Chemistry B. 118(31):9445-9459.
AbstractThe thermal behavior and transport properties of several ion jellys (IJs), a composite that results from the combination of gelatin with an ionic liquid (IL), were investigated by dielectric relaxation spectroscopy (DRS), differential scanning calorimetry (DSC), and pulsed field gradient nuclear magnetic resonance spectroscopy (PFG NMR). Four different ILs containing the dicyanamide anion were used: 1-butyl-3-methylimidazolium dicyanamide (BMIMDCA), 1-ethyl-3-methylimidazolium dicyanamide (EMIMDCA), 1-butyl-1-methylpyrrolidinium dicyanamide (BMPyrDCA), and 1-butylpyridinium dicyanamide (BPyDCA); the bulk ILs were also investigated for comparison. A glass transition was detected by DSC for all materials, ILs and IJs, allowing them to be classified as glass formers. Additionally, an increase in the glass transition temperature upon dehydration was observed with a greater extent for IJs, attributed to a greater hindrance imposed by the gelatin matrix after water removal, rendering the IL less mobile. While crystallization is observed for some ILs with negligible water content, it was never detected for any IJ upon thermal cycling, which persist always as fully amorphous materials. From DRS measurements, conductivity and diffusion coefficients for both cations (D+) and anions (D–) were extracted. D+ values obtained by DRS reveal excellent agreement with those obtained from PFG NMR direct measurements, obeying the same VFTH equation over a large temperature range (ΔT ≈ 150 K) within which D+ varies around 10 decades. At temperatures close to room temperature, the IJs exhibit D values comparable to the most hydrated (9%) ILs. The IJ derived from EMIMDCA possesses the highest conductivity and diffusion coefficient, respectively, 10–2 S·cm–1 and 10–10 m2·s–1. For BMPyrDCA the relaxational behavior was analyzed through the complex permittivity and modulus formalism allowing the assignment of the detected secondary relaxation to a Johari–Goldstein process. Besides the relevant information on the more fundamental nature providing physicochemical details on ILs behavior, new doorways are opened for practical applications by using IJ as a strategy to produce novel and stable electrolytes for different electrochemical devices.
Costa, Veigas, Bruno, Jacob, Jorge M., Santos, GMC, Santos, GMC, Baptista, Ana Catarina, Martins, Inacio, Joao, Fortunato E.
2014.
A low cost, safe, disposable, rapid and self-sustainable paper-based platform for diagnostic testing: lab-on-paper. Nanotechnology. 25(9):12pp..
Arcau, J, Andermark V, Aguiló E, Gandioso A, Moro A, Cetina M, Lima JC, Rissanen K, Ottb I, Rodríguez L.
2014.
Luminescent alkynyl-gold(I) coumarin derivatives and their biological activity. Dalton Transactions. 43:4426-4436.
AbstractLuminescent alkynyl-gold(I) coumarin derivatives and their biological activity
The synthesis and characterization of three propynyloxycoumarins are reported in this work together with the formation of three different series of gold(I) organometallic complexes. Neutral complexes are constituted by water soluble phosphines (PTA and DAPTA) which confer water solubility to them. The X-ray crystal structure of 7-(prop-2-in-1-yloxy)-1-benzopyran-2-one and its corresponding dialkynyl complex is also shown and the formation of rectangular dimers for the gold derivative in the solid state can be observed. A detailed analysis of the absorption and emission spectra of both ligands and complexes allows us to attribute the luminescent behaviour to the coumarin organic ligand. Moreover, the presence of the gold(I) metal atom seems to be responsible for an increase of coumarin phosphorescence emission. The biological activity of the complexes showed that the anionic complexes triggered strong cytotoxic effects in two different cell lines whereas the neutral gold alkynyl complexes led to lower effects against tumor cell growth. Thioredoxin reductase (TrxR) inhibition was very strong in the case of the neutral complexes (IC50 values below 0.1 μM) but moderate for the anionic complexes (IC50 values above 0.8 μM).