Petrov, V, Diniz AM, Cunha-Silva L, Parola AJ, Pina F.
2013.
Kinetic and thermodynamic study of 2 '-hydroxy-8-methoxyflavylium. Reaction network interconverting flavylium cation and flavanone, 2013. Rsc Advances. 3:10786-10794.
Abstract2'-Hydroxyflavylium and 2'-hydroxyflavanone derivatives can be interconverted by a precise sequence of pH jumps, through the respective intermediate (mono) ionized trans-chalcones. In acidic and neutral media, the well known network of chemical reactions involving flavylium cation, quinoidal base, hemiketal, and cis and trans chalcones is established. In the pH range 8 < pH < 10, the chalcone (Ct) deprotonates and evolves to the formation of a flavanone (F). At higher pH values, the di-ionized trans-chalcone is the stable species, formed from the flavylium cation. Acidification of the di-ionized trans-chalcone gives the flavylium cation or the flavanone, via the mono-ionized trans-chalcone, respectively at pH < 1 and pH approximate to 9. In contrast with the chalcones, the flavanone once formed is stable even in acidic media. However, under strongly basic conditions, it leads back to the di-ionized trans-chalcone, the most stable species at more basic pH values, and the reactions leading to Ct(-), F, Ct(2-), Ct(-), constitute a one direction cycle for interconversion of these species.
Coutinho, ML, Miller AZ, Gutierrez-Patricio S, Hernandez-Marine M, Gomez-Bolea A, Rogerio-Candelera MA, Philips AJL, Jurado V, Saiz-Jimenez C, Macedo MF.
2013.
Microbial communities on deteriorated artistic tiles from Pena National Palace (Sintra, Portugal), 2013. International Biodeterioration and Biodegradation. 84:322-332.
Abstractn/a
Calogero, G, Sinopoli A, Citro I, Di Marco G, Petrov V, Diniz AM, Parola AJ, Pina F.
2013.
Synthetic analogues of anthocyanins as sensitizers for dye-sensitized solar cells, 2013. Photochemical & Photobiological Sciences. 12:883-894.
AbstractSeven flavylium salt dyes were employed for the first time as sensitizers for dye-sensitized solar cells (DSSCs). The theoretical and experimental wavelengths of the maximum absorbances, the HOMO and LUMO energy levels, the coefficients, the oscillator strengths and the dipole moments are calculated for these synthetic dyes. The introduction of a donor group in the flavylium molecular structure was investigated. Photophysical and photoelectrochemical measurements showed that some of these synthetic analogues of anthocyanins are very promising for DSSC applications. The best performance was obtained by a DSSC based on the novel compound 7-(N,N-diethylamino)-3',4'-dihydroxyflavylium which produced a 2.15% solar energy-to-electricity conversion efficiency, under AM 1.5 irradiation (100 mW cm(-2)) with a short-circuit current density (J(sc)) of 12.0 mA cm(-2), a fill factor of 0.5 and an open-circuit voltage (V-oc) of 0.355 V; its incident photocurrent efficiency of 51% at the peak of the visible absorption band of the dye is remarkable. Our results demonstrated that the substitution of a hydroxylic group with a diethylamine unit in position 7 of ring A of the flavylium backbone expanded the pi-conjugation in the dye and thus resulted in a higher absorption in the visible region and is advantageous for effective electron injection from the dye into the conduction band of TiO2.
Silva, A, Luis D, Santos S, Silva J, Mendo AS, Coito L, Silva TF, da Silva MFG, Martins LM, Pombeiro AJ, Borralho PM, Rodrigues CM, Cabral MG, Videira PA, Monteiro C, Fernandes AR.
2013.
Biological characterization of the antiproliferative potential of Co(II) and Sn(IV) coordination compounds in human cancer cell lines: a comparative proteomic approach. Drug Metabol Drug Interact. 28(3):167-76.
C, N, M.P.F. G, M. E, B.A. S, R.C.C. M, L. R, T. M.
2013.
Effects of ultraviolet excitation on the spectroscopic properties of Sm3+ and Tb3+ doped aluminophosphate glasses. Optical Materials. 35(12):2382-2388.
AbstractLi2O–BaO–Al2O3–La2O3–P2O5 glasses optically activated with rare earth ions with the 4f5, and 4f8 electronic configuration (Sm3+ and Tb3+, respectively) were analyzed by Raman spectroscopy, absorption, excitation photoluminescence, decay curves and temperature dependent photoluminescence. The spectroscopic characteristics of the as-prepared and heat treated samples at temperatures below and above Tg were studied as well as their room temperature photometric properties under ultraviolet excitation. All the doped glasses exhibit typical signatures of the lanthanides in their trivalent charge state. For the samarium doped glass heat treated at 250 °C (lower than Tg) the Sm2+ luminescence was also observed. The analysis of the luminescence efficiency was performed in the interval range of 14 K to room temperature, where the integrated intensity of the luminescence was found to decrease for the Sm3+ and Tb3+ ions in the studied temperature range. Luminescence decay curves were found to be non-exponential for the 4G5/2 → 6H7/2 and5D3 → 7F4 transitions of the Sm3+ and Tb3+ ions, respectively. The results strongly suggest the occurrence of energy transfer processes through cross relaxation phenomena, mediated by dipole–dipole interaction in all the studied samples. The decay of the 5D4 → 7F5 emission of the Tb3+ ions was found to be single exponential with a time constant of ∼3.1 ms. Based on the spectroscopic characteristics, models for recombination processes are proposed. The room temperature luminance photometric properties with ultraviolet excitation show that the samarium doped glasses have much lower luminance intensity (around 0.3 Cd/m2) when compared with the 6–7 Cd/m2 observed for the terbium doped ones.
Carvalho, S, Raposo AC, Martins FB, Grosso AR, Sridhara SC, Rino J, Carmo-fonseca M, de Almeida SF.
2013.
Histone methyltransferase SETD2 coordinates FACT recruitment with nucleosome dynamics during transcription. Nucleic acids research. 41:2881–93., Number 5
AbstractHistone H3 of nucleosomes positioned on active genes is trimethylated at Lys36 (H3K36me3) by the SETD2 (also termed KMT3A/SET2 or HYPB) methyltransferase. Previous studies in yeast indicated that H3K36me3 prevents spurious intragenic transcription initiation through recruitment of a histone deacetylase complex, a mechanism that is not conserved in mammals. Here, we report that downregulation of SETD2 in human cells leads to intragenic transcription initiation in at least 11% of active genes. Reduction of SETD2 prevents normal loading of the FACT (FAcilitates Chromatin Transcription) complex subunits SPT16 and SSRP1, and decreases nucleosome occupancy in active genes. Moreover, co-immunoprecipitation experiments suggest that SPT16 is recruited to active chromatin templates, which contain H3K36me3-modified nucleosomes. Our results further show that within minutes after transcriptional activation, there is a SETD2-dependent reduction in gene body occupancy of histone H2B, but not of histone H3, suggesting that SETD2 coordinates FACT-mediated exchange of histone H2B during transcription-coupled nucleosome displacement. After inhibition of transcription, we observe a SETD2-dependent recruitment of FACT and increased histone H2B occupancy. These data suggest that SETD2 activity modulates FACT recruitment and nucleosome dynamics, thereby repressing cryptic transcription initiation.
Cerff, M, Scholz A, Franzreb M, Batalha IL, Roque ACA, Posten C.
2013.
In situ magnetic separation of antibody fragments from Escherichia coli in complex media. BMC biotechnology. 13(1):44.
AbstractBackground
In situ magnetic separation (ISMS) has emerged as a powerful tool to overcome process constraints such as product degradation or inhibition of target production. In the present work, an integrated ISMS process was established for the production of his-tagged single chain fragment variable (scFv) D1.3 antibodies (?D1.3?) produced by E. coli in complex media. This study investigates the impact of ISMS on the overall product yield as well as its biocompatibility with the bioprocess when metal-chelate and triazine-functionalized magnetic beads were used.
Results
Both particle systems are well suited for separation of D1.3 during cultivation. While the triazine beads did not negatively impact the bioprocess, the application of metal-chelate particles caused leakage of divalent copper ions in the medium. After the ISMS step, elevated copper concentrations above 120?mg/L in the medium negatively influenced D1.3 production. Due to the stable nature of the model protein scFv D1.3 in the biosuspension, the application of ISMS could not increase the overall D1.3 yield as was shown by simulation and experiments.
Conclusions
We could demonstrate that triazine-functionalized beads are a suitable low-cost alternative to selectively adsorb D1.3 fragments, and measured maximum loads of 0.08?g D1.3 per g of beads. Although copper-loaded metal-chelate beads did adsorb his-tagged D1.3 well during cultivation, this particle system must be optimized by minimizing metal leakage from the beads in order to avoid negative inhibitory effects on growth of the microorganisms and target production. Hereby, other types of metal chelate complexes should be tested to demonstrate biocompatibility. Such optimized particle systems can be regarded as ISMS platform technology, especially for the production of antibodies and their fragments with low stability in the medium. The proposed model can be applied to design future ISMS experiments in order to maximize the overall product yield while the amount of particles being used is minimized as well as the number of required ISMS steps.
Marcelo, F, Dias C, Madeira PJ, Jorge T, Florêncio HM, Canada JF, Cabrita EJ, Jiménez-Barbero J, Rauter AP.
2013.
Molecular Recognition of Rosmarinic Acid from Salvia sclareoides Extracts by Acetylcholinesterase: A New Binding Site Detected by NMR Spectroscopy. Chemistry: A European Journal. 19(21):6641–6649.
AbstractAcetylcholinesterase (AChE) inhibition is one of the most currently available therapies for the management of Alzheimer’s disease (AD) symptoms. In this context, NMR spectroscopy binding studies were accomplished to explain the inhibition of AChE activity by Salvia sclareoides extracts. HPLC-MS analyses of the acetone, butanol and water extracts eluted with methanol and acidified water showed that rosmarinic acid is present in all the studied samples and is a major constituent of butanol and water extracts. Moreover, luteolin 4′-O-glucoside, luteolin 3′,7-di-O-glucoside and luteolin 7-O-(6′′-O-acetylglucoside) were identified by MS2 and MS3 data acquired during the LC-MSn runs. Quantification of rosmarinic acid by HPLC with diode-array detection (DAD) showed that the butanol extract is the richest one in this component (134 μg mg−1 extract). Saturation transfer difference (STD) NMR spectroscopy binding experiments of S. sclareoides crude extracts in the presence of AChE in buffer solution determined rosmarinic acid as the only explicit binder for AChE. Furthermore, the binding epitope and the AChE-bound conformation of rosmarinic acid were further elucidated by STD and transferred NOE effect (trNOESY) experiments. As a control, NMR spectroscopy binding experiments were also carried out with pure rosmarinic acid, thus confirming the specific interaction and inhibition of this compound against AChE. The binding site of AChE for rosmarinic acid was also investigated by STD-based competition binding experiments using Donepezil, a drug currently used to treat AD, as a reference. These competition experiments demonstrated that rosmarinic acid does not compete with Donepezil for the same binding site. A 3D model of the molecular complex has been proposed. Therefore, the combination of the NMR spectroscopy based data with molecular modelling has permitted us to detect a new binding site in AChE, which could be used for future drug development.
C., C, M. R, C.M. S, J.J.G. M, E. O, E. J, M.G. A.
2013.
Nitrite biosensing using cytochrome c nitrite reductase: Towards a disposable strip electrode. Biomedical Engineering Systems and Technologies, Communications in Computer and Information Science. :41-51., DOI:10.1007/978-3-642-38256-7_3: Springer, Heidelberg
Ramos, A.M., Pereira, Cidade, M.T., Pereira, Branquinho, R., Pereira, Martins, Fortunato E.
2013.
Preparation and characterization of cellulose nanocomposite hydrogels as functional electrolytes. Solid State Ionics. 242:26-32.