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Gas-phase interactions between Ba2+ and deprotonated cytosine (C(−H)) were studied in [C(−H)Ba]+ and [C(−H)BaC]+ complexes by IRMPD spectroscopy coupled to tandem mass-spectrometry in combination with DFT calculations. For the [C(−H)BaC]+ complex only one [C(−H)KAN1O−Ba-Canti]+ isomer was found, although the presence of another structure cannot be excluded. This isomer features a central tetracoordinated Ba2+ that simultaneously interacts with keto-amino [C(−H)]− deprotonated on N1 and neutral keto-amino C. Both moieties are in different planes as a consequence of an additional NH…O=C hydrogen bond between C and [C(−H)]−. A sequential IRMPD dynamics is observed in this complex. For the [C(−H)Ba]+ complex produced by electrospray ionization two isomers ([C(−H)KAN1OBa]+ and [C(−H)KAN3OBa]+) were identified, in which Ba2+ interacts simultaneously with the C=O group and the N1 or N3 atom of the keto-amino [C(−H)]−, respectively. A comparison with the related [C(−H)Pb]+ complex (J. Y. Salpin et al., Chem. Phys. Chem. 2014, 15, 2959–2971) is also presented. Fil: Cruz Ortiz, Andres Felipe. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Taccone, Martín Ignacio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Maitre, Philippe. Universite de Paris XI. Laboratoire de Chimie Physique; Francia Fil: Rossa, Maximiliano. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Pino, Gustavo Ariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina

In this paper, we present the IRMPD spectra of three ionic complexes between guanine (G) and silver (Ag+): [GAg-H2O]+, [GAgG]+ produced in the electrospray ionization source of the mass spectrometer, and [GAg]+ produced by collision induced dissociation of the [GAgG]+ complex. On the basis of the comparison of theoretically calculated IR spectra, we show that there are two isomers of each complex containing two different keto-amino (KA) tautomers of G (GKA(1,9) and GKA(1,7)). The observed isomers are the most stable structures in aqueous solution, and their experimentally estimated relative populations are in better agreement with the calculated relative populations in solution than in the gas phase, both at 298 K. We concluded that these observations suggest that GKA(1,9) and GKA(1,7) coexist in solution according to previous theoretical reports (Colominas, C.; et al. J. Am. Chem. Soc. 1996, 118, 6811). We were unable to find any evidence of the presence of the GEA(9), GKA(3,7), GKA(3,9), or GKA(7,9), whose relative stabilities in solution are strongly dependent on the theoretical method used to account for the solvent effect (Hanus, M.; et al. J. Am. Chem. Soc. 2003, 125, 7678).

International audience; The sodium/iodide symporter (NIS) expresses at the basolateral plasma membrane of the thyroid follicular cell and mediates iodide accumulation required for normal thyroid hormonogenesis. Loss-of-function NIS variants cause congenital hypothyroidism due to impaired iodide accumulation in thyroid follicular cells underscoring the significance of NIS for thyroid physiology. Here we report novel findings derived from the thorough characterization of the nonsense NIS mutant p.R636* NIS-leading to a truncated protein missing the last eight amino acids-identified in twins with congenital hypothyroidism. R636* NIS is severely mislocalized into intracellular vesicular compartments due to the lack of a conserved carboxy-terminal type 1 PDZ-binding motif. As a result, R636* NIS is barely targeted to the plasma membrane and therefore iodide transport is reduced. Deletion of the PDZ-binding motif causes NIS accumulation into late endosomes and lysosomes. Using PDZ domain arrays, we revealed that the PDZ-domain containing protein SCRIB binds to the carboxy-terminus of NIS by a PDZ-PDZ interaction. Furthermore, in CRISPR/Cas9-based SCRIB deficient cells, NIS expression at the basolateral plasma membrane is compromised, leading to NIS localization into intracellular vesicular compartments. We conclude that the PDZ-binding motif is a plasma membrane retention signal that participates in the polarized expression of NIS by selectively interacting with the PDZ-domain containing protein SCRIB, thus retaining the transporter at the basolateral plasma membrane. Our data provide insights into the molecular mechanisms that regulate NIS expression at the plasma membrane, a topic of great interest in the thyroid cancer field considering the relevance of NIS-mediated radioactive iodide therapy for differentiated thyroid carcinoma.

Tocochromanols constitute the different forms of vitamin E (VTE), essential components of the human diet, and display a high membrane protectant activity. By combining interval mapping and genome-wide association studies (GWAS), we unveiled the genetic determinants of tocochromanol accumulation in tomato (Solanum lycopersicum) fruits. To enhance the nutritional value of this highly consumed vegetable, we dissected the natural intraspecific variability of tocochromanols in tomato fruits and genetically engineered their biosynthetic pathway. These analyses allowed the identification of a total of 25 quantitative trait loci interspersed across the genome pinpointing the chorismate–tyrosine pathway as a regulatory hub controlling the supply of the aromatic head group for tocochromanol biosynthesis. To validate the link between the chorismate–tyrosine pathway and VTE, we engineered tomato plants to bypass the pathway at the arogenate branch point. Transgenic tomatoes showed moderate increments in tocopherols (up to approximately 20%) and a massive accumulation of tocotrienols (up to approximately 3400%). Gene expression analyses of these plants reveal a trade-off between VTE and natural variation in chorismate metabolism explained by transcriptional reprogramming of specific structural genes of the pathway. By restoring the accumulation of alpha-tocotrienols (α-t3) in fruits, the plants produced here are of high pharmacological and nutritional interest. Fil: Burgos, Estanislao. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Fisiología, Biología Molecular y Neurociencias. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Fisiología, Biología Molecular y Neurociencias; Argentina Fil: de Luca, Maria Belén. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Fisiología, Biología Molecular y Neurociencias. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Fisiología, Biología Molecular y Neurociencias; Argentina Fil: Diouf, Isidore. Centre Nouvelle - Aquitaine Bordeaux ; Instituto National de Recherches Agronomiques, Alimetation Et Environnement; Fil: de Haro, Luis Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Fisiología, Biología Molecular y Neurociencias. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Fisiología, Biología Molecular y Neurociencias; Argentina Fil: Albert, Elise. Michigan State University; Estados Unidos. Centre Nouvelle - Aquitaine Bordeaux ; Instituto National de Recherches Agronomiques, Alimetation Et Environnement; Fil: Sauvage, Christopher. Centre Nouvelle - Aquitaine Bordeaux ; Instituto National de Recherches Agronomiques, Alimetation Et Environnement; . Syngenta France SAS; Francia Fil: Tao, Zhao J.. Centre Nouvelle - Aquitaine Bordeaux ; Instituto National de Recherches Agronomiques, Alimetation Et Environnement; Fil: Bermudez Salazar, Luisa Fernanda. Instituto Nacional de Tecnología Agropecuaria. Centro Regional Buenos Aires; Argentina. Universidad de Buenos Aires. Facultad de Agronomía; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Asís, Ramon. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Córdoba. Centro de Investigaciones en Bioquímica Clínica e Inmunología; Argentina Fil: Nesi, Adriano N.. Universidade Federal de Viçosa.; Brasil Fil: Matringe, Michel. Universite Joseph Fourier; Francia. Centre Nouvelle - Aquitaine Bordeaux ; Instituto National de Recherches Agronomiques, Alimetation Et Environnement; Fil: Bréhélin, Claire. Universite Joseph Fourier; Francia. Centre Nouvelle - Aquitaine Bordeaux ; Instituto National de Recherches Agronomiques, Alimetation Et Environnement; Fil: Guiraud, Thomas. Universite de Bordeaux; Francia. Centre Nouvelle - Aquitaine Bordeaux ; Instituto National de Recherches Agronomiques, Alimetation Et Environnement; Fil: Ferrand, Carine. Universite de Bordeaux; Francia. Centre Nouvelle - Aquitaine Bordeaux ; Instituto National de Recherches Agronomiques, Alimetation Et Environnement; Fil: Atienza, Isabelle. Universite de Bordeaux; Francia. Centre Nouvelle - Aquitaine Bordeaux ; Instituto National de Recherches Agronomiques, Alimetation Et Environnement; Fil: Jorly, Joana. Universite de Bordeaux; Francia. Centre Nouvelle - Aquitaine Bordeaux ; Instituto National de Recherches Agronomiques, Alimetation Et Environnement; Fil: Mauxion, Jean P.. Universite de Bordeaux; Francia. Centre Nouvelle - Aquitaine Bordeaux ; Instituto National de Recherches Agronomiques, Alimetation Et Environnement; Fil: Baldet, Pierre. Centre Nouvelle - Aquitaine Bordeaux ; Instituto National de Recherches Agronomiques, Alimetation Et Environnement; . Universite de Bordeaux; Francia Fil: Fernie, Alisdair R.. Institut Max Planck fur Molekulare Physiologie; Alemania Fil: Quadrana, Leandro. Inserm; Francia. Centre National de la Recherche Scientifique; Francia Fil: Rothan, Christophe. Universite de Bordeaux; Francia. Centre Nouvelle - Aquitaine Bordeaux ; Instituto National de Recherches Agronomiques, Alimetation Et Environnement; Fil: Causse, Mathilde. Centre Nouvelle - Aquitaine Bordeaux ; Instituto National de Recherches Agronomiques, Alimetation Et Environnement; Fil: Carrari, Fernando Oscar. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Fisiología, Biología Molecular y Neurociencias. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Fisiología, Biología Molecular y Neurociencias; Argentina. Universidad de Buenos Aires; Argentina

The present study reports the first structural characterization of protonated cyameluric acid ([CA + H]+) in the gas phase, which paves the way for prospective bottom-up research on the condensed-phase chemistry of CA in the protonated form. A number of [CA + H]+ keto-enol isomers can a priori be produced as a result of protonation at available N and O positions of precursor neutral CA tautomers, yet ab initio computations predict different reduced [CA + H]+ isomer populations dominating the solution and gas phases that are involved in the ion generation process (i.e., electrospray ionization). Infrared multiple photon dissociation spectra were recorded in the 990-1900 and 3300-3650 cm-1 regions and compared with theoretical [B3LYP/6-311++G(d,p)] IR absorption spectra of several [CA + H]+ isomers, providing a satisfactory agreement for the most stable monohydroxy form in the gas phase, [1358a]+, yet the contribution of its nearly isoenergetic OH rotamer, [1358b]+, cannot be neglected. This is indicative of the occurrence of [CA + H]+ isomer interconversion reactions, assisted by protic solvent molecules, during their transfer into the gas phase. The results suggest that available O positions on neutral CA are energetically favored protonation sites in the gas phase.

The rate coefficients for the reactions of OH with ethanol and n-propanol were determined by a relative method in a smog chamber at 294 K, 1 atm of air or N2 and a wide range of humidity. The rate coefficients for both reactions show a quadratic dependence on the water concentration as in the case of the reaction of OH with methanol (Jara-Toro et al. Angew. Chem., Int. Ed., 2017, 56, 2166). The detailed mechanism responsible for the reaction acceleration was studied theoretically at the uMP2/aug-cc-pVDZ level of theory while the electronic energies of all the structures were refined at the uCCSD(T)/aug-cc-pVDZ level. From these results it is suggested that the catalytic effect of two water molecules is due to two cooperative effects in the reactions between the ROH(H2O) and OH(H2O) equilibrium complexes: (1) an enhanced capture cross-section as a consequence of the larger dipolar moment of the ROH(H2O) and OH(H2O) complexes as compared to those of the free reactants ROH and OH and (2) a strong stabilization of the TSs below the energy of the reactants that leads to a very fast decomposition of the pre-reactive complexes to products with an extremely low probability of dissociation back to the reactants. The tropospheric lifetime of these alcohols is also shown to strongly depend on the humidity, suggesting the need to incorporate this dependence in global atmospheric models. Fil: Jara Toro, Rafael Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Hernadez, Federico Javier. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Garavagno, Maria de Los Angeles. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Taccone, Raul Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Pino, Gustavo Ariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina

In this work, we investigate the degradation process of 1-chlorobutane, initiated by OH radicals, under atmospheric conditions (air pressure of 750 Torr and 296 K) from both experimental and theoretical approaches. In the first one, a relative kinetic method was used to obtain the rate coefficient for this reaction, while the products were identified for the first time (1-chloro-2-butanone, 1-chloro-2-butanol, 4-chloro-2-butanone, 3-hydroxy-butanaldehyde, and 3-chloro-2-butanol) using mass spectrometry, allowing suggesting a reaction mechanism. The theoretical calculations, for the reactive process, were computed using the BHandHLYP/6-311++G(d,p) level of theory, and the energies for all of the stationary points were refined at the CCSD(T) level. Five conformers for 1-chlorobutane and 33 reactive channels with OH radicals were found, which were considered to calculate the thermal rate coefficient (as the sum of the site-specific rate coefficients using canonical transition state theory). The theoretical rate coefficient (1.8 × 10-12 cm3 molecule-1 s-1) is in good agreement with the experimental value (2.22 ± 0.50) × 10-12 cm3 molecule-1 s-1 determined in this work. Finally, environmental impact indexes were calculated and a discussion on the atmospheric implications due to the emissions of this compound into the troposphere was given. Fil: Jara Toro, Rafael Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Barrera, Javier Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Aranguren Abrate, Juan Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Taccone, Raúl A.. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Pino, Gustavo Ariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina

International audience; While aromatic amino acids in their deprotonated form have been well characterized by IR and photoelectron spectroscopies, no information is available on the neutral dehydrogenated protonated radicals and, in particular, on their stability when the deprotonation site is changed. This is investigated by observing the neutral fragment issued from either simple photodetachment or dissociative photodetachment of the deprotonated aromatic amino acids phenylalanine, tyrosine, and tryptophan. We show that the dehydrogenated radicals of aromatic amino acids produced upon photodetachment of molecules deprotonated on the carbonyl group dissociate without barrier, leading to the formation of CO 2 and a radical amine. However, when the system is deprotonated on functional groups located on the chromophore, the radicals produced by photodetachment are stable, indicating the important photostabilizing role played by functional groups.

The UV photofragmentation spectra of cold cytosine-M+ complexes (M+: Na+, K+, Ag+) were recorded and analyzed through comparison with geometry optimizations and frequency calculations of the ground and excited states at the SCS-CC2/Def2-SVPD level of theory. While in all complexes, the ground state minimum geometry is planar (Cs symmetry), the ππ* state minimum geometry has the NH2 group slightly twisted and an out-of-plane metal cation. This was confirmed by comparing the simulated ππ* Franck-Condon spectra with the vibrationally resolved photofragmentation spectra of CytNa+ and CytK+. Vertical excitation transitions were also calculated to evaluate the energies of the CT states involving the transfer of an electron from the Cyt moiety to M+. For both CytK+ and CytNa+ complexes, the first CT state corresponds to an electron transfer from the cytosine aromatic π ring to the antibonding σ* orbital centered on the alkali cation. This πσ* state is predicted to lie much higher in energy (>6 eV) than the band origin of the π-π* electronic transition (around 4.3 eV) unlike what is observed for the CytAg+ complex for which the first excited state has a nOσ* electronic configuration. This is the reason for the absence of the Cyt+ + M charge transfer fragmentation channel for CytK+ and CytNa+ complexes.

Polycrystalline Sr2Fe1+xRe1-xO6 samples have been synthesized and structurally characterized by X-ray powder diffraction, transmission electron microscopy and X-ray absorption spectroscopy. Resistivity strongly increases with x, but a large and negative magnetoresistance persists up to x = 0.33. This is discussed considering the charge delocalization in iron and rhenium t2g orbitals. Fil: Maignan, Antoine. Ecole Nationale Superieure D'ingenieurs de Caen; Francia Fil: Martin, Christine. Ecole Nationale Superieure D'ingenieurs de Caen; Francia Fil: Lebedev, Oleg. Ecole Nationale Superieure D'ingenieurs de Caen; Francia Fil: Sottmann, Jonas. Ecole Nationale Superieure D'ingenieurs de Caen; Francia Fil: Nataf, Lucie. Soleil Synchrotron; Francia Fil: Baudelet, François. Soleil Synchrotron; Francia Fil: Hébert, Sylvie. Soleil Synchrotron; Francia Fil: Carbonio, Raul Ernesto. Universidad Nacional de Córdoba; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina

International audience; The competition between dissociative photodetachment and photodissociation of cold benzoate and naphthoate anions was studied through measurement of the kinetic energy of the neutral fragments and intact parent benzoyloxy and naphtoyloxy radicals as well as by detecting the anionic fragments whenever they are produced. For the benzoate anion, there is no ionic photodissociation and the radical dissociation occurs near the vertical photodetachment energy. This is in agreement with DFT calculations showing that the dissociation energy in CO2 and C6H5˙ is very low. The dissociation barrier can be deduced from experimental results and calculations to be (0.7 ± 0.1) eV, which makes the benzoyloxyradical C6H5COO˙ very unstable, although more stable than the acetyloxy radical. In the case of naphthoate, the observation of negative fragments at low excitation energies demonstrates the opening of the ionic photodissociation channel in the excited state of the naphthoate anion, whose yield decreases at higher energies when the dissociative photodetachment channel opens.

A novel approach for the synthesis of tetracyclic indoles and 7-azaindoles is reported. The strategy involves four steps, with a fast rt intramolecular α-arylation of ketones as key step. The reaction was inspected synthetically to achieve the synthesis of 11 novel tetracyclic structures with moderate to very good yields (39-85%). Theoretical combined with experimental studies led us to propose a probable polar mechanism (concerted S

The rate coefficient of the cis-3-hexene + Cl atoms reaction at 296 ± 2 K and 750 ± 10 Torr was determined using the relative rate technique. The reaction was investigated using an 80 L Teflon reaction bag and a gas chromatograph coupled with flame-ionization detection. Chlorine atoms were produced by the photolysis of trichloroacetyl chloride. No previous experimental data was available in the literature, to the best of our knowledge. The mean second-order rate coefficient value found was (4.13 ± 0.51) × 10-10 cm3 molecule-1 s-1. The experimental value agrees with the rate coefficient estimated by structure-reactivity analysis, 4.27 × 10-10 cm3 molecule-1 s-1. Moreover, both addition and hydrogen abstraction channels contribute to the global kinetics, with branching ratios 70:30. Effective lifetime with respect to Cl atoms is predicted as 67.2 hours; however, the cis-3-hexene + Cl channel is suggested to be non-negligible at atmospheric conditions. Other atmospheric implications are discussed. Fil: Barbosa, Thaís S.. Universidade Federal Rural do Rio de Janeiro; Brasil Fil: Barrera, Javier Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Jara Toro, Rafael Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Bauerfeldt, Glauco F.. Universidade Federal Rural do Rio de Janeiro; Brasil Fil: Arbilla, Graciela. Universidade Federal do Rio de Janeiro; Brasil Fil: Lane, Silvia Irene. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina

Charge transfer reactions are ubiquitous in chemical reactivity and often viewed as ultrafast processes. For DNA, femtochemistry has undeniably revealed the primary stage of the deactivation dynamics of the locally excited state following electronic excitation. We here demonstrate that the full time scale excited state dynamics can be followed up to milliseconds through an original pump-probe photodissociation scheme applied to cryogenic ion spectroscopy. Protonated cytosine is chosen as a benchmark system in which the locally excited 1ππ∗ state decays in the femtosecond range toward long-lived charge transfer and triplet states with lifetimes ranging from microseconds to milliseconds, respectively. A three-step mechanism (1ππ∗ → 1CT → 3ππ∗) is proposed where internal conversion from each state can occur leading ultimately to fragmentation in the ground electronic state. Fil: Broquier, Michel. Université Paris Sud; Francia Fil: Soorkia, Satchin. Université Paris Sud; Francia Fil: Pino, Gustavo Ariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Dedonder-Lardeux, Claude. Marseille Université; Francia Fil: Jouvet, Christophe. Marseille Université; Francia Fil: Grégoire, Gilles. Université Paris Sud; Francia

Recently, DNA molecules have received great attention because of their potential applications in material science. One interesting example is the production of highly fluorescent and tunable DNA–Agn clusters with cytosine (C)-rich DNA strands. Here, we report the UV photofragmentation spectra of gas-phase cytosine···Ag+···cytosine (C2Ag+) and cytosine···H+···cytosine (C2H+) complexes together with theoretical calculations. In both cases, the excitation energy does not differ significantly from that of isolated cytosine or protonated cytosine, indicating that the excitation takes place on the DNA base. However, the excited-state lifetime of the C2H+ (τ = 85 fs), estimated from the bandwidth of the spectrum, is at least 2 orders of magnitude shorter than that of the C2Ag+ (τ > 5000 fs). The increased excited-state lifetime upon silver complexation is quite unexpected, and it clearly opens the question about what factors are controlling the nonradiative decay in pyrimidine DNA bases. This is an important result for the expanding field of metal-mediated base pairing and may also be important to the photophysical properties of DNA-templated fluorescent silver clusters. Fil: Berdakin, Matias. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Féraud, Geraldine. Aix Marseille Université. Marsella; Francia Fil: Dedonder Lardeux, Claude. Aix Marseille Université. Marsella; Francia Fil: Jouvet, Christophe. Aix Marseille Université. Marsella; Francia Fil: Pino, Gustavo Ariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina

The rate coefficient for the reaction CH3OH+OH was determined by means of a relative method in a simulation chamber under quasi-real atmospheric conditions (294 K, 1 atm of air) and variable humidity or water concentration. Under these conditions, a quadratic dependence of the rate coefficient for the reaction CH3OH+OH on the water concentration was found. Thus the catalytic effect of water is not only important at low temperatures, but also at room temperature. The detailed mechanism responsible of the reaction acceleration is still unknown. However, this dependence should be included in the atmospheric global models since it is expected to be important in humid regions as in the tropics. Additionally, it could explain several differences regarding the global and local atmospheric concentration of methanol in tropical areas, for which many speculations about the sinks and sources of methanol have been reported. Fil: Jara Toro, Rafael Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Hernández, Federico Javier. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Taccone, Raul Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Lane, Silvia Irene. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Pino, Gustavo Ariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina

The gas phase structure and excited state lifetime of the p-aminophenol⋯p-cresol heterodimer have been investigated by REMPI and LIF spectroscopy with nanosecond laser pulses and pump-probe experiments with picosecond laser pulses as a model system to study the competition between p-p and H-bonding interactions in aromatic dimers. The excitation is a broad and unstructured band. The excited state of the heterodimer is long lived (2.5 ± 0.5) ns with a very broad fluorescence spectrum red-shifted by 4000 cm-1 with respect to the excitation spectrum. Calculations at the MP2/RI-CC2 and DFT-ωB97X-D levels indicate that hydrogen-bonded (HB) and p-stacked isomers are almost isoenergetic in the ground state while in the excited state only the p-stacked isomer exists. This suggests that the HB isomer cannot be excited due to negligible Franck-Condon factors and therefore the excitation spectrum is associated with the p-stacked isomer that reaches vibrationally excited states in the S1 state upon vertical excitation. The excited state structure is an exciplex responsible for the fluorescence of the complex. Finally, a comparison was performed between the p-stacked structure observed for the p-aminophenol. . .p-cresol heterodimer and the HB structure reported for the (p-cresol)2 homodimer indicating that the differences are due to different optical properties (oscillator strengths and Franck-Condon factors) of the isomers of both dimers and not to the interactions involved in the ground state. Fil: Capello, Marcela Carolina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Hernández, Federico Javier. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Broquier, Michel. Université Paris Sud; Francia Fil: Dedonder-Lardeux, Claude. Aix-Marseille Université; Francia Fil: Jouvet, Cristophe. Aix-Marseille Université; Francia Fil: Pino, Gustavo Ariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina

The gas phase structure and excited state dynamics of o-aminophenol-H2O complex have been investigated using REMPI, IR-UV hole-burning spectroscopy, and pump–probe experiments with picoseconds laser pulses. The IR-UV spectroscopy indicates that the isomer responsible for the excitation spectrum corresponds to an orientation of the OH bond away from the NH2 group. The water molecule acts as H-bond acceptor of the OH group of the chromophore. The complexation of o-aminophenol with one water molecule induced an enhancement in the excited state lifetime on the band origin. The variation of the excited state lifetime of the complex with the excess energy from 1.4 ± 0.1 ns for the 0–0 band to 0.24 ± 0.3 ns for the band at 0–0 + 120 cm–1 is very similar to the variation observed in the phenol-NH3 system. This experimental result suggests that the excited state hydrogen transfer reaction is the dominant channel for the non radiative pathway. Indeed, excited state ab initio calculations demonstrate that H transfer leading to the formation of the H3O• radical within the complex is the main reactive pathway. Fil: Hernández, Federico Javier. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Capello, Marcela Carolina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Naito, Ayumi. Tokyo Institute of Technology; Japón Fil: Manita, Shun. Tokyo Institute of Technology; Japón Fil: Tsukada, Kohei. Tokyo Institute of Technology; Japón Fil: Miyazaki, Mitsuhiko. Tokyo Institute of Technology; Japón Fil: Fujii, Masaaki. Tokyo Institute of Technology; Japón Fil: Broquier, Michel. Université Paris Sud; Francia Fil: Gregoire, Gabriel Eduardo. Université Paris Sud; Francia Fil: Dedonder Lardeux, Claude. Aix Marseille Université; Francia Fil: Jouvet, Christophe. Aix Marseille Université; Francia Fil: Pino, Gustavo Ariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina

Neopterin is found at increased levels in biological fluids from individuals with inflammatory disorders. The biological role of this pteridine remains undefined; however, due to its capacity to increase hemeoxygenase-1 content, it has been proposed as a protective agent during cellular stress. Therefore, we investigated the effects of neopterin on motor, emotional and memory functions. To address this question, neopterin (0.4 and/or 4 pmol) was injected intracerebroventricularly before or after the training sessions of step-down inhibitory avoidance and fear conditioning tasks, respectively. Memory-related behaviors were assessed in Swiss and C57BL/6 mice, as well as in Wistar rats. Moreover, the putative effects of neopterin on motor and anxiety-related parameters were addressed in the open field and elevated plus-maze tasks. The effects of neopterin on cognitive performance were also investigated after intraperitoneal lipopolysaccharide (LPS) administration (0.33 mg/kg) in interleukin-10 knockout mice (IL-10-/-). It was consistently observed across rodent species that neopterin facilitated aversive memory acquisition by increasing the latency to step-down in the inhibitory avoidance task. This effect was related to a reduced threshold to generate the hippocampal long-term potentiation (LTP) process, and reduced IL-6 brain levels after the LPS challenge. However, neopterin administration after acquisition did not alter the consolidation of fear memories, neither motor nor anxiety-related parameters. Altogether, neopterin facilitated cognitive processes, probably by inducing an antioxidant/anti-inflammatory state, and by facilitating LTP generation. To our knowledge, this is the first evidence showing the cognitive enhancer property of neopterin. Fil: Ghisoni, Karina. Universidade Federal de Santa Catarina; Brasil Fil: Aguiar, Aderbal S.. Universidade Federal de Santa Catarina; Brasil Fil: Oliveira, Paulo Alexandre de. Universidade Federal de Santa Catarina; Brasil Fil: Matheus, Filipe Carvalho. Universidade Federal de Santa Catarina; Brasil Fil: Gabach, Laura. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Farmacología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Farmacología Experimental de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Farmacología Experimental de Córdoba; Argentina Fil: Perez, Mariela Fernanda. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Farmacología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Farmacología Experimental de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Farmacología Experimental de Córdoba; Argentina Fil: Carlini, Valeria Paola. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Ciencias de la Salud. Universidad Nacional de Córdoba. Instituto de Investigaciones en Ciencias de la Salud; Argentina Fil: Barbeito, Luis. Instituto Pasteur de Montevideo; Uruguay Fil: Mongeau, Raymond. Université Paris Descartes. INSERM UMR. Centre de Psychiatrie et Neurosciences; Francia Fil: Lanfumey, Laurence. Umr S894, Centre de Psychiatrie Et Neurosciences; Francia Fil: Prediger, Rui Daniel. Universidade Federal de Santa Catarina; Brasil Fil: Latini, Alexandra. Universidade Federal de Santa Catarina; Brasil

We are presenting the electronic photo fragment spectra of the protonated pyrimidine DNA bases homo-dimers. Only the thymine dimer exhibits a well structured vibrational progression, while protonated monomer shows broad vibrational bands. This shows that proton bonding can block some non radiative processes present in the monomer., We acknowledge the use of the computing facility cluster GMPCS of the LUMAT federation (FR LUMAT 2764)

The very fast relaxation of the excited states to the ground state in DNA/RNA bases is a necessary process to ensure the photostability of DNA and its rate is highly sensitive to the tautomeric form of the bases. Protonation of the bases plays a crucial role in many biochemical and mutagenic processes and it can result in alternative tautomeric structures, thus making important the knowledge of the properties of protonated DNA/RNA bases. We report here the photofragmentation spectra of the five protonated DNA/RNA bases. In most of the cases, the spectra exhibit well resolved vibrational structures, with broad bands associated with very short excited state lifetimes. The similarity between the electronic properties, e.g. excitation energy and very short excited state lifetimes for the canonical tautomers of protonated and neutral DNA bases, suggests that the former could also play an important role in the photostability mechanism of DNA. Fil: Berdakin, Matias. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Féraud, Geraldine. Aix Marseille Université. Marsella; Francia Fil: Dedonder Lardeux, Claude. Aix Marseille Université. Marsella; Francia Fil: Jouvet, Christophe. Aix Marseille Université. Marsella; Francia Fil: Pino, Gustavo Ariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina

The gas phase structure of 2-aminophenol has been investigated using UV–UV as well as IR–UV hole burning spectroscopy. The presence of a free OH vibration in the IR spectrum rules out the contribution of the cis isomer, which is expected to have an intramolecular H-bond, to the spectra. The excited state lifetimes of different vibronic levels have been measured with pump–probe picosecond experiments and are all very short (35 ± 5) ps as compared to other substituted phenols. The electronic states and active vibrational modes of the cis and trans isomers have been calculated with ab initio methods for comparison with the experimental spectra. The Franck–Condon simulation of the spectrum using the calculated ground and excited state frequencies of the trans isomer is in good agreement with the experimental one. The very short excited state lifetime of 2-aminophenol can then be explained by the strong coupling between the two first singlet excited states due to the absence of symmetry, the geometry of the trans isomer being strongly nonplanar in the excited state. Fil: Capello, Marcela Carolina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Broquier, Michel. Universite Paris Sud; Francia Fil: Ischiuchi, Shun-Ichi. Tokyo Institute of Technology. Yokohama; Japón Fil: Sohn, Woon Y.. Tokyo Institute of Technology. Yokohama; Japón Fil: Fujii, Masaaki. Tokyo Institute of Technology. Yokohama; Japón Fil: Dedonder Lardeux, Claude. Aix-Marseille Universite; Francia Fil: Jouvet, Christophe. Aix-Marseille Universite; Francia Fil: Pino, Gustavo Ariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina

The rate constant of the reaction (R1)OH+CH3O2→products has been measured at 294 K by simultaneous coupling of Laser Induced Fluorescence (LIF) and cw-Cavity Ring Down Spectroscopy (cw-CDRS) to laser photolysis. OH radicals were generated by 248 nm photolysis of either H2O2 or O3 in the presence of H2O, CH3O2 radicals were generated simultaneously by photolysis of CH3I and their absolute concentrations were obtained by cw-CRDS. OH decays were measured under excess CH3O2 concentrations and a very fast rate constant of k1 = (2.8 ± 1.4) 1010 cm3 s1 was found independent of pressure at 50 and 100 Torr helium. Fil: Bossolasco, Adriana Gabriela. University Lille I; Francia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Faragó, Eszter P.. University Lille I; Francia. University of Szeged; Hungría Fil: Schoemaecker, Coralie. University Lille I; Francia Fil: Fittschen, Christa. University Lille I; Francia

The excited state dynamics of the H-bonded 7-azaindole-phenol complex (7AI-PhOH) has been studied by combination of picosecond pump and probe experiments, LIF measurements on the nanosecond time scale and ab initio calculations. A very short S1 excited state lifetime (30 ps) has been measured for the complex upon excitation of the 00 0 transition and the lifetime remains unchanged when the ν6 vibrational mode (00 0 + 127 cm−1) is excited. In addition, no UV-visible fluorescence was observed by exciting the complex with nanosecond pulses. Two possible deactivation channels have been investigated by ab initio calculations: first an excited state tautomerization assisted by a concerted double proton transfer (CDPT) and second an excited state concerted proton electron transfer (CPET) that leads to the formation of a radical pair (hydrogenated 7AIH• radical and phenoxy PhO• radical). Both channels, CDPT and CPET, seem to be opened according to the ab initio calculations. However, the analysis of the ensemble of experimental and theoretical evidence indicates that the excited state tautomerization assisted by CDPT is quite unlikely to be responsible for the fast S1 state deactivation. In contrast, the CPET mechanism is suggested to be the non-radiative process deactivating the S1 state of the complex. In this mechanism, the lengthening of the OH distance of the PhOH molecule induces an electron transfer from PhOH to 7AI that is followed by a proton transfer in the same kinetic step. This process leads to the formation of the radical pair (7AIH•···PhO•) in the electronically excited state through a very low barrier or to the ion pair (7AIH+···PhO−) in the ground state. Moreover, it should be noted that, according to the calculations the πσ* state, which is responsible for the H loss in the free PhOH molecule, does not seem to be involved at all in the quenching process of the 7AI-PhOH complex. Fil: Capello, Marcela Carolina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Broquier, Michel. Universite Paris Sud; Francia Fil: Dedonder Lardeux, Claude. Universite Paris Sud; Francia Fil: Jouvet, Christophe. Universite Paris Sud; Francia Fil: Pino, Gustavo Ariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina

International audience; Lifetimes of the first electronic excited state (S(1)) of fluorine and methyl (o-, m-, and p-) substituted phenols and their complexes with one ammonia molecule have been measured for the 0(0) transition and for the intermolecular stretching σ(1) levels in complexes using picosecond pump-probe spectroscopy. Excitation energies to the S(1) (ππ*) and S(2) (πσ*) states are obtained by quantum chemical calculations at the MP2 and CC2 level using the aug-cc-pVDZ basis set for the ground-state and the S(1) optimized geometries. The observed lifetimes and the energy gaps between the ππ* and πσ* states show a good correlation, the lifetime being shorter for a smaller energy gap. This propensity suggests that the major dynamics in the excited state concerns an excited state hydrogen detachment or transfer (ESHD/T) promoted directly by a S(1)/S(2) conical intersection, rather than via internal conversion to the ground-state. A specific shortening of lifetime is found in the o-fluorophenol-ammonia complex and explained in terms of the vibronic coupling between the ππ* and πσ* states occurring through the out-of-plane distortion of the C-F bond.

The photo-induced damages of DNA in interaction with metal cations, which are found in various environments, still remain to be characterized. In this paper, we show how the complexation of a DNA base (cytosine (Cyt)) with a metal cation (Ag+) changes its electronic properties. By means of UV photofragment spectroscopy of cold ions, it was found that the photoexcitation of the CytAg+ complex at low energy (315-282) nm efficiently leads to ionized cytosine (Cyt+) as the single product. This occurs through a charge transfer state in which an electron from the p orbital of Cyt is promoted to Ag+, as confirmed by ab initio calculations at the TD-DFT/B3LYP and RI-ADC(2) theory level using the SV(P) basis set. The low ionization energy of Cyt in the presence of Ag+ could have important implications as point mutation of DNA upon sunlight exposition. Fil: Taccone, Martín Ignacio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Féraud, Geraldine. Aix Marseille Université. Physique des Interactions Ioniques et Moléculaires; Francia Fil: Berdakin, Matias. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Dedonder Lardeux, Claude. Aix Marseille Université. Physique des Interactions Ioniques et Moléculaires; Francia Fil: Jouvet, Christophe. Physique des Interactions Ioniques et Moléculaires; Francia Fil: Pino, Gustavo Ariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina

14 p.-4 fig.-2 tab.- 8 schem., We prepared a series of free NH and N-substituted dibenzonthiazines with potential anti-tumor activity from N-aryl-benzenesulfonamides. A biological test of synthesized compounds (59 samples) was performed in vitro measuring their antiproliferative activity against a panel of six human solid tumor cell lines and its tubulin inhibitory activity. We identified 6-(phenylsulfonyl)-6H-dibenzo[c,e][1,2]thiazine 5,5-dioxide and 6-tosyl-6H-dibenzo[c,e][1,2]thiazine 5,5-dioxide as the best compounds with promising values of activity (overall range of 2-5.4 μM). Herein, we report the dibenzothiazine core as a novel building block with antiproliferative activity, targeting tubulin dynamics., This study was supported by Agencia Córdoba Ciencia,Consejo Nacional de Investigaciones Científicas y Técnicas(CONICET),Secretaría de Ciencia y Tecnología,Universidad Nacional de Córdoba (SECyT),and Agencia Nacional de Promoción Científica y Técnica(ANPCyT).W. D. G. gratefully acknowledge receipt of fellowship from CONICET.J. M. P. thanks the Spanish Government for financial support through project PGC2018-094503-B-C22(MCIU/AEI/FEDER,UE). The biochemical work was supported by grants Ministerio de Ciencia e Innovación PID2019-104545RB-I00/AEI/10.13039/501100011033,PIEs 201920E111 and 202020E301 from Consejo Superior de Investigaciones Científicas,grant “Bases moleculares de la regulación de microtúbulos y sus implicaciones en la neurotoxicidad producida por fármacos ”from Fundación TATIANA and European Union H2020-MSCA-ITN-2019 860070TUBINTRAIN grant to JFDP and a generous donation from Club Deportivo Escuela Hungaresa de Pontevedra.

Fil: Paredes Mellone, Oscar Ariel. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnologico Conicet - Cordoba. Instituto de Fisica Enrique Gaviola. Universidad Nacional de Cordoba. Instituto de Fisica Enrique Gaviola; Argentina. Universidad Nacional de Cordoba. Facultad de Matematica, Astronomia y Fisica; Argentina

26 páginas.- 28 figuras.- 71 referencias, Deracemisation methods have demonstrated their importance in the preparation of chiral compounds in the last few years. In order to resolve a racemic mixture in a dynamic sense, one enantiomer of the starting material can be converted to the other through a deracemisation procedure, that can be achieved by different mechanisms based on stereoinversion or enantioconvergence, often involving two‐opposite half reactions, with at least one of the reactions being enantioselective enough to finally obtain an enantioenriched chiral compound. The focus of this comprehensive review is on the application of deracemisation procedures in the present century in order to obtain optically active valuable compounds when employing non‐metallic catalysts. Thus, the review will mainly focus on the use of different enzymatic preparations (purified enzymes, cell‐free extracts or whole cell systems) and organocatalysts for the deracemisation of racemic mixtures., We thank Martin G. López-Vidal for his collaboration.G.d.G. thanks MINECO for Ramón y Cajal Program and CTQ2016-76908-C2-1,2-P projects. G.O-M. and F.R.B. ac-knowledge INFIQC-CONICET and Universidad Nacionalde Cordoba (UNC) and also thank FONCyT as well asSECyT-UNC for research funding.

Vicuna is a wild, endangered species of Andean camelid living in the hyperarid Andean plateau. In the central part of the plateau, the Lithium Triangle defines a zone with lithium‐rich salt pans. Brine pools naturally form within the salt pans, and the adaptation strategy of vicuna consists of drinking from brine pools. Together with reporting the first chemical data on vicuna bones and teeth, we analyzed lithium, boron, and arsenic in water and brines, with the aim of assessing their relation to chronic exposure by water ingestion. We collected and analyzed bones of vicuna specimens lying in an Andean salt pan, together with brine and water samples. Brine and water samples are highly saline and contain large amounts of lithium, boron, and arsenic. Lithium (13.50–40 mg kg–1 ) and boron (40–46.80 mg kg–1 ), but not arsenic, were found in the vicuna bones and teeth. Based on our results and on previously reported data on human tissues in the Andes, we conducted statistical assessments of the relationships between lithium and boron in body tissues and water samples, and discuss their environmental significance in the context of the Lithium Triangle. Fil: López Steinmetz, Romina Lucrecia. Universidad Nacional de Jujuy. Instituto de Ecorregiones Andinas. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Salta. Instituto de Ecorregiones Andinas; Argentina. Universidad Nacional de Jujuy. Instituto de Geología Minera; Argentina Fil: Fong, Shao Bing. University of Melbourne; Australia Fil: Boyer, Emile. Universite de Rennes I; Francia Fil: López Steinmetz, Lorena Cecilia. Universidad Nacional de Córdoba. Instituto de Investigaciones Psicológicas. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones Psicológicas; Argentina Fil: Tejerina, Norberto Elio. Universidad Nacional de Jujuy. Instituto de Geología Minera; Argentina Fil: Meuric, Vincent. Universite de Rennes I; Francia

We report here an impedimetric genosensor for the quantification of microRNA-21 using [Fe(CN)6]3−/4− as redox probe to transduce the hybridization event. The biosensing platform was built at a thiolated-gold electrode by covalent bond of reduced graphene oxide (RGO) modified with chitosan (CHIT) and further covalent attachment of the aminated DNA probe. GO was used to provide the carboxylic groups for the covalent attachment of CHIT and, once reduced, to improve the electroactivity of the resulting platform, while CHIT served as a bridge between the thiol and the aminated probe DNA. The proposed bioanalytical platform allows the label-free, non-amplified, simple and fast biosensing of microRNA-21, with a linear range between 1.0 × 10−12 M and 1.0 × 10−8 M, a sensitivity of (134 ± 4) ΩM−1 (r2 = 0.996), a detection limit of 300 fM, and a reproducibility of 5.9% for 1.0 × 10−12 M miRNA-21 and 2.2% for 1.0 × 10−9 M miRNA-21. The genosensor was successfully used for the quantification of microRNA-21 in enriched human blood serum, urine and saliva samples.

International audience; Furfural has been considered as one of the most promising platform molecules directly derived from biomass. The hydrogenation of furfural is one of the most versatile reactions to upgrade furanic components to biofuels. For instance, it can lead to plenty of downstream products, such as (tetrahydro)furfuryl alcohol, 2-methyl(tetrahydro)furan, lactones, levulinates, cyclopentanone(l), or diols, etc. The aim of this review is to discuss recent advances in the catalytic hydrogenation of furfural towards (tetrahydro)furfuryl alcohol and 2-methyl(tetrahydro)furan in terms of different non-noble metal and noble metal catalytic systems. Reaction mechanisms that are related to the different catalytic materials and reaction conditions are properly discussed. Selective hydrogenation of furfural could be modified not only by varying the types of catalyst (nature of metal, support, and preparation method) and reaction conditions, but also by altering the reaction regime, namely from batch to continuous flow. In any case, furfural catalytic hydrogenation is an open research line, which represents an attractive option for biomass valorization towards valuable chemicals and fuels.

International audience; The reaction mechanism for the formation of alkyl thiol self-assembled monolayers (SAM) on Au(111) is still not clearly understood. Especially, the role of defects on the chemisorption process is an important goal to be addressed. In this work, different minimum energy reaction paths for R−SH dissociation of thiols (with long and short chains and dithiol species) adsorbed on gold adatom are calculated by using periodic density functional theory (DFT). Our results show a lower energy barrier for the RS−H bond dissociation when two thiols are adsorbed per adatom. In addition, in contrast with the formation of an adatom at the Au(111) which has been shown to depend on the alkyl chain length, the activation energy of the RS−H bond dissociation of thiols adsorbed on an adatom was shown to be independent of the alkyl chain length. The presented results and derived hypothesis support the model that thiols with long alkyl chain thiols mainly adsorb molecularly on Au(111), while for short alkyl chain thiols the S−H bond breaks. This result is explained by the fact that short-chain thiols have lower interchain interaction energies and are thus more mobile compared to the long alkyl chain thiols on the Au(111) surface. This feature enables the short chains to reach adequate geometries, driven by entropy, which could deform the Au(111) more drastically and probably pull Au atoms out from surface to form adatoms. With these results a new mechanism is proposed for the formation of alkyl chain thiols on Au(111).

Different phase diagram measurements for succinonitrile-camphor alloys to date have yielded different values of the solute partition coefficient and the freezing range of the alloy. These parameters are critical to model solidification microstructure evolution. New measurements are made to precisely characterize the dilute limit of the succinonitrile-camphor phase diagram using thin-sample directional solidification experiments where convection is negligible, so that solute transport in the melt is purely diffusive, and the temperature gradient is constant in time. These results are confirmed through complementary measurements by differential scanning calorimetry and isothermal annealing. Possible measurement uncertainties in previously measured solidus lines are discussed. Experimental results were further confirmed using a boundary layer model of transient planar interface dynamics. Fil: Mota, F. L.. Aix-Marseille Université; Francia. Centre National de la Recherche Scientifique; Francia. Iowa State University; Estados Unidos Fil: Fabietti, Luis Maria Rodolfo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; Argentina Fil: Bergeon, N.. Aix-Marseille Université; Francia. Centre National de la Recherche Scientifique; Francia Fil: Strutzenberg, L. L.. Marshall Space Flight Center; Estados Unidos Fil: Karma, A.. Northeastern University; Estados Unidos Fil: Billia, B.. Aix-Marseille Université; Francia. Centre National de la Recherche Scientifique; Francia Fil: Trivedi, R.. Iowa State University; Estados Unidos

Innate immune activation and chronic neuroinflammation are characteristic features of many neurodegenerative diseases including Parkinson´s disease (PD) and may contribute to the pathophysiology of the disease. The discovery of misfolded alpha-synuclein (αSYN) protein aggregates, which amplify in a ?prion-like? fashion, has led us to consider that pathogenic αSYN might be hijacking the activation and mobilization mechanism of the peripheral immune system to reach and disseminate within the CNS. Furthermore, our lab and other groups have recently shown that αSYN can adopt distinct fibril conformations or ?strains? with varying levels of pathogenic impact. Therefore, the aim of this study was to assess the impact of peripheral inflammation on αSYN spreading in order to better understand the participation of the immune system in the progression of PD. The results presented here show that intraperitoneal LPS injection prior to systemic intravenous recombinant administration of two different αSYN pathogenic strains (fibrils or ribbons) in wild type mice, induces an increase in brain resident microglia and promotes the recruitment of leukocytes toward the brain and the spinal cord. Our findings show for the first time that αSYN can be internalized by LPS-primed inflammatory monocytes, which in turn favors the dissemination from the periphery toward the brain and spinal cord. Further, we found a differential recruitment of CD4+ and CD8+ T cells after LPS priming and subsequent administration of the αSYN ribbons strain. Together, these data argue for a role of the peripheral immune system in αSYN pathology. Fil: Peralta Ramos, Javier María. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Córdoba. Centro de Investigaciones en Bioquímica Clínica e Inmunología; Argentina Fil: Iribarren, Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Córdoba. Centro de Investigaciones en Bioquímica Clínica e Inmunología; Argentina Fil: Bousset, Luc. Institut François Jacob; Francia Fil: Melki, Ronald. Institut François Jacob; Francia Fil: Baekelandt, Veerle. Katholikie Universiteit Leuven; Bélgica Fil: Van der Perren, Anke. Katholikie Universiteit Leuven; Bélgica

Lung carcinoma is one of the most common cancers and has a high mortality. Recently, we showed that it produces neurological paraneoplastic syndrome, with Ilex paraguariensis (IP) extract exerting palliative effects due to its content of phenolic compounds. It is possible, therefore, that these diet agents can arrive at the brain and exert neuroprotection, after the oral intake of IP. Here, the aim was to investigate the protective role of bioavailable IP compounds on the telencephalon and diencephalon in lung adenocarcinoma-bearing BALB/cJ males. Mice aged 2 months were treated for 3 weeks with 0-100 IP mg·kg-1 ·day-1 . HPLC-UV revealed the presence of chlorogenic acid and quercetin in brain regions, liver, and tumour, in an IP dose-dependent manner. Brain was also evaluated histologically, and interleukin-6 was measured by ELISA. Chlorogenic acid was the major compound found in brain, whereas quercetin was observed at the diencephalon to a lesser extent. Both compounds were involved in IP dose-dependent diencephalic interleukin-6 reduction. Histology suggested cellular protection with less apoptosis in chlorogenic-exposed areas. Taken together, chlorogenic acid and quercetin from dietary IP were bioavailable and bioactive in brain, thereby attenuating lung cancer-related neuroinflammation and damage. These findings support plant-based strategies to improve prognosis., Financial support: SECYT ‐ Universidad Nacional de Córdoba (grant 313/2016), INYM and CONICET (grant 4342/2016 22320160100044CO), Argentina; Ministerio de Economía, Industria y Competitividad (I+D+I Retos Program grant AGL2016‐76832‐R), Spain.

11 p.-9 fig.-3 tab., Numerous studies have highlighted the implications of the glycogen synthase kinase 3 (GSK-3) in several processes associated with Alzheimer's disease (AD). Therefore, GSK-3 has become a crucial therapeutic target for the treatment of this neurodegenerative disorder. Hereby, we report the design and multistep synthesis of ethyl 4-oxo-pyrazolo[4,3-d][1-3]triazine-7-carboxylates and their biological evaluation as GSK-3 inhibitors. Molecular modelling studies allow us to develop this new scaffold optimising the chemical structure. Potential binding mode determination in the enzyme and the analysis of the key features in the catalytic site are also described. Furthermore, the ability of pyrazolotriazinones to cross the blood-brain barrier (BBB) was evaluated by passive diffusion and those who showed great GSK-3 inhibition and permeation to the central nervous system (CNS) showed neuroprotective properties against tau hyperphosphorylation in a cell-based model. These new brain permeable pyrazolotriazinones may be used for key in vivo studies and may be considered as new leads for further optimisation for the treatment of AD., Funding from MINECO (grant no. SAF2016-76693-R to A.M.) and MEC (FPU15/1465 to VSP.), CONICET and SECYT-UNC are also acknowledged.

Mammalian glycosaminoglycans are linear complex polysaccharides comprising heparan sulfate, heparin, dermatan sulfate, chondroitin sulfate, keratan sulfate and hyaluronic acid. They bind to numerous proteins and these interactions mediate their biological activities. GAG–protein interaction data reported in the literature are curated mostly in MatrixDB database (http://matrixdb. univ-lyon1.fr/). However, a standard nomenclature and a machine-readable format of GAGs together with bioinformatics tools for mining these interaction data are lacking. We report here the building of an automated pipeline to (i) standardize the format of GAG sequences interacting with proteins manually curated from the literature, (ii) translate them into the machine-readable GlycoCT format and into SNFG (Symbol Nomenclature For Glycan) images and (iii) convert their sequences into a format processed by a builder generating three-dimensional structures of polysaccharides based on a repertoire of conformations experimentally validated by data extracted from crystallized GAG–protein complexes. We have developed for this purpose a converter (the CT23D converter) to automatically translate the GlycoCT code of a GAG sequence into the input file required to construct a three-dimensional model.

This work aims at the development of an electrochemical affinity biosensor for Pb(II) quantification using a platform that combines glassy carbon electrodes (GCE) and an aqueous dispersion of single-walled carbon nanotubes (SWCNT) covalently modified with cysteine residues (Cys). The biosensing protocol includes the accumulation of Pb(II) at the electrode surface through the affinity interaction promoted by Cys residues at open circuit potential, followed by the reduction of the accumulated Pb(II) at ‐0.900 V and the transduction step performed by linear sweep-adsorptive stripping voltammetry (LSAdSV) in a 0.020 M acetate buffer solution pH 5.00. There is a linear relationship between Pb(II) oxidation peak current and Pb(II) concentration. The dynamic linear range extends from 5.0 to 125.0 μg·L−1, exhibiting a sensitivity of 0.061 μAμg−1L and a detection limit of 0.69 μg·L−1. In addition, the selectivity of the biosensor was evaluated in the presence of high concentrations of possible interferents such as Cu(II), Cd(II), Ni(II), Hg(II), Rh(II), Ru(II), Zn(II), Ir(IV), Co(II) and As(III) demonstrating a high discrimination of Pb(II) in complex samples. The sensor was challenged with tap and rain water samples enriched with Pb(II), demonstrating outstanding properties in terms of recovery percentages showing an excellent agreement with ICP- MS., The authors are grateful to CONICET (PIP 2015 Project N° 11220150100710CO), SECyT-UNC (PID Project 2016-2017 SIGEVA N° 30720150101013CB), ANPCyT (Projects : PICT 2013 N° 2817, PICT 2015 N° 0077) and MINCyT-Córdoba (PID Project N° 000018/2014), Spanish Ministry of Economy and Competitiveness (MINECO) project ENE2013-48816-C5-5-R, and the Government of Aragon and the European Social Fund under project grant DGA-FSE-T66 CNN for the financial support given to this work. M.L.R. and C.S.T. acknowledge doctoral fellowships from CONICET.

7 Figuras.- 3 Tablas, This work is focused on the development of an electrochemical sensor for the quantification of Cd(II) based on the use of glassy carbon electrodes (GCE) modified with a dispersion of single-walled carbon nanotubes (SWCNTs) covalently functionalized with cysteine (Cys). Cd(II) is preconcentrated at the electrode surface by complex formation at open circuit potential, followed by the reduction at ∧0.900 V and the final anodic voltammetric stripping in a 0.020 M acetate buffer solution pH 5.00. The functionalization of SWCNTs was performed through the reaction between the carboxylic groups of oxidized SWCNT and amino groups of S-triphenylmethyl cysteine using a coupling chemistry agent based on benzotriazol for the activation of carboxylic residues. There was a linear relationship between Cd oxidation signal and Cd(II) concentration between 1.0 and 300.0 α/4gL∧1 Cd(II), with a sensitivity of (49 ± 2) í 10∧3 α/4Aα/4g∧1L and a detection limit of 0.3 α/4gL∧1. The reproducibility was 1.7% using the same dispersion and 3.8% using 3 different dispersions. The sensor was challenged with groundwater samples enriched with Cd(II) showing excellent recovery percentages and excellent agreement with the values obtained by ICP-MS., The authors thank CONICET, SECyT-UNC, ANPCyT, MINCyT-Córdoba, Spanish Ministry of Economy and Competitiveness (MINECO) project ENE2013-48816-C5-5-R, and the Government of Aragon and the European Social Fund under project grant DGA-FSE-T66 CNN for the financial support.

A combination of XPS, in situ RAIRS, LEED, and STM experiments together with ab initio DFT calculations were used to elucidate the self-assembly properties at the atomic level, and enabled the interpretation of the expression of surface chirality upon adsorption of both enantiomers of methionine on a clean Au(111) surface under UHV conditions. The combination of experimental results, in particular, LEED and STM data with quantum chemical calculations is shown to be a successful setup strategy for addressing this challenge. It was found that the methionine molecular self-assembly consists of the first molecule lying parallel to the gold surface and the second interacting with the first methionine through a 2D H-bond network. The interaction with the gold surface is weak. The stability of the assembly is mainly due to the presence of intermolecular H bonds, resulting in the formation of ziplike dimer rows on the Au(111) surface. The methionine molecules interact with each other via their amino acid functional groups. The assembly shows an asymmetric pattern due to a slightly different orientation of the methionine molecules with respect to the surface. Simulations of the STM image of methionine assemblies were consistent with the experimental STM image. The present study shows another example of Au(111) stabilizing a self-assembled biological layer, which is not chemically perturbed by the surface.

Hydrogen interaction with bimetallic Au(Pd) and Au(Rh) systems are studied with the density functional theory (DFT)-based periodic approach. Several bimetallic configurations with varying concentrations of Pd and Rh atoms in the under layer of a gold surface(111) were considered. The reactivity of the doped Au(111) toward hydrogen adsorption and absorption was related to the property modifications induced by the presence of metal dopants. DFT-computed quantities, such as the energy stability, the inter-atomic and inter-slab binding energies between gold and dopants, and the charge density were used to infer the similarities and differences between both Pd and Rh dopants in these model alloys. The hydrogen penetration into the surface is favored in the bimetallic slab configurations. The underlayer dopants affect the reactivity of the surface gold toward hydrogen adsorption in the systems with a dopant underlayer, covered by absorbed hydrogen up to a monolayer. This indicates a possibility to tune the gold surface properties of bimetallic electrodes by modulating the degree of hydrogen coverage of the inner dopant layer(s) Fil: Juarez, Maria Fernanda. Universidad de Ulm; Alemania. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Soldano, Germán. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina. Universidad de Ulm; Alemania Fil: Santos, Elizabeth del Carmen. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; Argentina Fil: Guesmi, Hazar. Institut Charles Gerhardt Montpellier; Francia Fil: Tielens, Frederik. Universite de Paris I Pantheon - Sorbonne; Francia Fil: Mineva, Tzonka. Institut Charles Gerhardt Montpellier; Francia

Ternary chalcogenides (ABX) based on the spinel structure are gaining a great deal of attention because of the possibility of tuning their magnetic and optoelectronic properties not only by changing chemical composition but also by altering their degree of inversion. Here we report a rapid high-pressure synthetic method for the synthesis of MInS powders starting from commercially available solid sulfides. We prove the versatility of our method by reporting the synthesis of six members of the MInS family (M = Mn, Fe, Co, Ni, Zn, and Cd) under high-pressure conditions (3.5 GPa); these compounds show complete to moderate degrees of inversion. Furthermore, this family covers a spectral region that includes visible band gaps. Interestingly, the structural refinement carried out by X-ray and neutron diffraction allows one to establish positive correlations between the gap and different parameters, including the degree of inversion. Finally, as a proof-of-concept, these ternary chalcogenides show moderate photocatalytic hydrogen production from aqueous solutions., The authors thank the Spanish Ministerio de Economía y Com-petitividad (MINECO) for financial support through the projectsMAT2013-41099-R, CTQ2013-48669-P, and MAT2014-54994-R.R. E. C. acknowledges support from the Consejo Nacionalde Investigaciones Científicas y Técnicas (CONICET) (PIP#11220120100360), the Agencia Nacional de Promoción Científ-ica y Tecnológica (ANPCyT) (PICT-2013-2149), and the Secretariade Ciencia y Tecnología de la Universidad Nacional de Cordoba(SECyT-UNC) (project 203/14). J. P.B. is grateful for a fellowshipfrom CONICET. MINECO/ICTI2013-2016/CTQ2013-48669-P MINECO/ICTI2013-2016/MAT2014-54994-R

The intestinal epithelium regulates the transit of molecules from and into the organism. Several agents act as absorption enhancers inducing changes in both transcellular and paracellular routes. Chitosan is a non-toxic biocompatible polysaccharide widely used as dietary supplement and mucosal delivery. Chitosan triggers both the activation of intestinal epithelial cells and the release of regulatory factors relevant for its immunomodulatory activity. Yet, the interaction of chitosan with intestinal epithelial cells is poorly characterized. We studied the uptake of this polysaccharide, and we evaluated its effects in both the net water and ion movements across human and rat colon samples and the epithelial permeability. Herein, we demonstrate that chitosan increases the transcellular permeability to ions, water and protein markers in human and rat intestinal mucosa and decreases the water permeability across the paracellular pathway. These findings are relevant to understand the activity of the polysaccharide in the mucosal environment., This work was supported by grants of CONICET, Agencia Nacional de Promoción Cientifica y Tecnológica (FONCYT), Ministerio de Ciencia y Tecnología de Córdoba and SECyT-UNC. MMC and LPP are CONICET and FONCYT fellows, respectively. CI and SGC belong to the research staff of CONICET.

66-3 FIELD Section Title:Surface Chemistry and Colloids UMR 7197, and CNRS, UMR 7197, Laboratoire de Reactivite de Surface, UPMC Univ Paris 06, Paris, Fr. FIELD URL: written in English; The bonding of propanethiol mols. on a Au(111) surface is studied using period DFT calcns. within the framework of the model for chem. bond breaking that was recently proposed. The S-H bond breaking and the Au-S bond formation are analyzed through the evolution of the d. of states. The energetics confirms the complexity of the reaction emerging from the interthiol chain interaction. The formation of a self-assembled monolayer is explained through a two-step mechanism, S-H bond breaking and Au-S bond formation. The prodn. of H2 is more favorable than the formation of Au-H species. The bonding and antibonding electronic states of the S-H bond were identified and their evolutions during the process of bond breaking carefully analyzed. The corresponding bonding and antibonding states for the C-S bond are practically not affected during this process, indicating that the bond is preserved. The s orbital of the hydrogen atom strongly interacts with the gold surface and finally a Au-H bond is formed. [on SciFinder(R)]

This work is aimed at studying the adsorption mechanism of short chain 20-mer pyrimidinic homoss-DNA (oligodeoxyribonucleotide, ODN: polyC20 and polyT20) onto CNT by reflectometry. To analyze the experimental data, the effective-medium theory using the Bruggemann approximation represents a suitable optical model to account for the surface properties (roughness, thickness, and optical constants) and the size of the adsorbate. Systematic information about the involved interactions is obtained by changing the physicochemical properties of the system. Hydrophobic and electrostatic interactions are evaluated by comparing the adsorption on hydrophobic CNT and on hydrophilic silica and by modulating the ionic strength with and without Mg2+. The ODN adsorption process on CNT is driven by hydrophobic interactions only when the electrostatic repulsion is suppressed. The adsorption mode results in ODN molecules in a side-on orientation with the bases (nonpolar region) toward the surface. This unfavorable orientation is partially reverse by adding Mg2+. On the other hand, the adsorption on silica is dominated by the strong repulsive electrostatic interaction that is screened at high ionic strength or mediated by Mg2+. The cation-mediated process induces the interaction of the phosphate backbone (polar region) with the surface, leaving the bases free for hybridization. Although the general adsorption behavior of the pyrimidine bases is the same, polyC20 presents higher affinity for the CNT surface due to its acid-base properties., Authors acknowledge the financial contributions of FONCyT, SeCyT-UNC, CONICET, the International Exchange Collaboration between CAPES (Brazil) and SPU (Argentine) (Grant No. 025/05), and National Institute of General Medical Sciences (NIGMS)/National Institutes of Health (1SC3GM081085) (C.D.G). M.J.E. thanks the Ministry of Education and Science of Spain (Project NAN2004-093006-C05-03) and the “Ramón and Cajal” Program. M.L.C. thanks CONICET for the fellowship granted.

7 Figuras,1 Tabla, This work reports the synthesis and characterization of single-walled carbon nanotubes (SWCNT) covalently functionalized with L-lysine (Lys) and the analytical performance of glassy carbon electrodes (GCE) modified with a dispersion of SWCNT-Lys (GCE/SWCNT-Lys) for the highly sensitive quantification of guanine, adenine and 8-hydroxy-2′-deoxyguanosine. Detection limits of 75, 195 and 97 nM were obtained for guanine, adenine and 8-hydroxy-2′-deoxyguanosine, respectively by voltammetric adsorptive stripping with medium exchange. GCE/SWCNT-Lys was successfully used for the detection of adenine and guanine oxidation after adsorption of salmon sperm-double stranded DNA. A clear definition of 8-hydroxy-2′-deoxyguanosine oxidation signal is observed even in the presence of large excess of guanine, adenine or salmon sperm-double stranded DNA., The authors thank CONICET, SECyT-UNC, ANPCyT, MINCyTC Córdoba for the financial support. AG and ME thanks CONICET for the fellowship received.

The dissolution behavior of montroydite (HgO) has been studied using a fully automated system. Dissolution data under equilibrium conditions are in agreement with previously published data and indicate that HgO solubility is relatively high and constant between pH 4 and 10.1 and increases markedly at pH < 4. The dissolution rate also has similar behavior: it is relatively high and constant between pH 4 and 10.1 and increases sharply at pH < 4. The dissolution process obeys a three-dimensional contraction or attrition mechanism. The dissolution rate increases with increasing temperature and stirring rate and is the result of mixed transport and reaction control. The rate of HgO dissolution is considerably higher than that of other divalent metal oxides at low pH. This high rate is due to the ability of Hg(II) to rapidly exchange its ligands. Data suggest that montroydite will only occur in nature in highly contaminated sites and indicate that Hg oxidation products that are formed at the liquid Hg/water interface may dissolve rapidly. Fil: Hocsman, Ana. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Fisicoquímica; Argentina Fil: Di Nezio, Maria Susana. Universidad Nacional del Sur. Departamento de Química; Argentina Fil: Charlet, Laurent. University of Grenoble; Francia Fil: Avena, Marcelo Javier. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; Argentina

Bimetallic catalysts have manifold technological applications; their reactivity can greatly exceed that of the original single metals. In this work, we investigate an ideal model-system consisting of a complete monolayer of Pd underneath the surface of Au(111). First, we investigate the stability of this system, and then its interaction with hydrogen. We analyze in detail the energetics and the electronic interactions for the Volmer step of the hydrogen evolution reaction (HER), and the further absorption below the surface layer of gold. We combine Density Functional Theory based on computational techniques with the theory of electrocatalysis. Fil: Juarez, Maria Fernanda. Universitat Ulm; Alemania. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Soldano, Germán. Universitat Ulm; Alemania. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Guesmi, Hazar. Institut Charles Gerhardt Montpellier; Francia Fil: Tielens, Frederik. Universite Pierre et Marie Curie; Francia Fil: Santos, Elizabeth del Carmen. Universitat Ulm; Alemania. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; Argentina

Long-chain flavodoxins, ubiquitous electron shuttles containing flavin mononucleotide (FMN) as prosthetic group, play an important protective role against reactive oxygen species (ROS) in various microorganisms. Pseudomonas aeruginosa is an opportunistic pathogen which frequently has to face ROS toxicity in the environment as well as within the host. We identified a single ORF, hereafter referred to as fldP (for flavodoxin from P . aeruginosa), displaying the highest similarity in length, sequence identity and predicted secondary structure with typical long-chain flavodoxins. The gene was cloned and expressed in Escherichia coli. The recombinant product (FldP) could bind FMN and exhibited flavodoxin activity in vitro. Expression of fldP in P. aeruginosa was induced by oxidative stress conditions through an OxyR-independent mechanism, and an fldP-null mutant accumulated higher intracellular ROS levels and exhibited decreased tolerance to H2O2 toxicity compared to wild-type siblings. The mutant phenotype could be complemented by expression of a cyanobacterial flavodoxin. Overexpression of FldP in a mutT-deficient P. aeruginosa strain decreased H2O2-induced cell death and the hypermutability caused by DNA oxidative damage. FldP contributed to the survival of P. aeruginosa within cultured mammalian macrophages and in infected Drosophila melanogaster, which led in turn to accelerated death of the flies. Interestingly, the fldP gene is present in some but not all P. aeruginosa strains, constituting a component of the P. aeruginosa accessory genome. It is located in a genomic island as part of a self-regulated polycistronic operon containing a suite of stress-associated genes. The collected results indicate that the fldP gene encodes a long-chain flavodoxin, which protects the cell from oxidative stress, thereby expanding the capabilities of P. aeruginosa to thrive in hostile environments., Author Summary Coping with toxic reactive oxygen species (ROS) generated as by-products of aerobic metabolism is a major challenge for O2-thriving organisms, which deploy multilevel responses to prevent ROS-triggered damage, including membrane modifications, induction of antioxidant and repair systems and/or replacement of ROS-sensitive targets by resistant isofunctional versions, among others. The opportunistic pathogen Pseudomonas aeruginosa is frequently exposed to ROS in the environment as well as within the host, and we describe herein a new response by which this microorganism can deal with oxidative stress. This pathway depends on a previously uncharacterized gene that we named fldP (for flavodoxin from P . aeruginosa), which encodes a flavoprotein that belongs to the family of long-chain flavodoxins. FldP exhibited a protective role against ROS-dependent physiological and mutational damage, and contributed to the survival of P. aeruginosa during in vivo infection of flies as well as within mammalian macrophagic cells. Thus, fldP increases the adaptive repertoire of P. aeruginosa to face oxidative stress.