BUSCADOR RECOLECTA

A theoretical study of the effect of the diprotonation on the nucleic acid bases (A : U, A : T and G : C) in Watson‐Crick conformation has been carried out by means of DFT computational methods in vacuum. In addition, the corresponding neutral and monoprotonated binary complexes have been considered. Most of the diprotonated species studied are stable, even though the binding energy is positive due to the overall repulsive electrostatic term. Local electrostatic attractive forces in the regions of hydrogen bonds (HBs) are responsible for equilibrium geometries, as shown by the electric field lines connecting the electrophilic and nucleophilic sites involved in the HB interactions. Secondary electrostatic effects also affect the assembling of the nucleic acid complexes in either neutral or cationic form. In particular, the electric field lines flowing from electrophilic sites in one base to nucleophilic sites in the other reinforce the linking between them. Hence, when the nucleophilic site concerns the free lone pair of the heteroatom involved in the HB interaction as acceptor, the HB distance shortens. However, if the free lone pair of the HB acceptor interacts with an electrophilic site in the same molecule, the HB distance elongates, weakening the HB interaction. The topological analysis of the electron density distribution in HB regions indicates that neutral, monoprotonated and diprotonated complexes show no differences in the nature of their HB's., This work was supported by the Spanish Ministerio de Economía y Competitividad (Grants CSD2007‐00041, ENE2015‐63969‐C3‐3‐R, SEV2015‐0496 and CTQ2015‐63997‐C2‐2‐P), the Catalan Government (Grant PRC 2017SGR‐1687), the Autonomous Community of Madrid (Grant Fotocarbon and S2013/MIT‐2841) and the French ANR project ANR‐17‐CE07‐0025‐01., Peer reviewed

In this work, we report the cocrystallization of N⁹-ethyladenine with 1,2,4,5-tetrafluoro-3,6-diiodobenzene (TFDIB), a classical XB donor. As far as our knowledge extends, this is the first cocrystal reported to date where an adenine derivative acts as a halogen bond acceptor. In the solid state, each adenine ring forms two centrosymmetric H-bonded dimers: one using N1···HA6–N6 and the other N7···HB6–N6. Therefore, only N3 is available as a halogen bond acceptor that, indeed, establishes an N···I halogen bonding interaction with TFDIB. The H-bonded dimers and halogen bonds have been investigated via DFT (Density Functional Theory) calculations and the Bader’s Quantum Theory of Atoms In Molecules (QTAIM) method at the B3LYP/6-311+G* level of theory. The influence of H-bonding interactions on the lone pair donor ability of N3 has also been analyzed using the molecular electrostatic potential (MEP) surface calculations., This research was funded by MINECO/AEI from Spain, project numbers ENE2015-63969, CTQ2017-85821-R FEDER and SEV2015-0496, We acknowledge support by the CSIC Open Access Publication Initiative through its Unit of Information Resources for Research (URICI), Peer reviewed

Co-doped titanium dioxide was synthesized by doping with manganese (Mn) and cerium (Ce) through a sol-gel method for the degradation of diclofenac (DCF). The synthesized products were successfully characterized by X-ray diffraction (XRD), Raman spectroscopy, Transmission electron microscopy (TEM), Scanning electron microscopy (SEM), Nitrogen physisorption at 77 K, X-ray photoelectron spectroscopy (XPS), UV–Vis diffuse reflectance (UV-DRS), photoluminescence spectroscopy (PL) and total organic carbon (TOC). It was shown that co-doping increased the specific surface area, improved the visible light absorption and extended the lifetime of photogenerated charge carriers. Furthermore, the results of the photocatalytic experiments show that the photodegradation rate of diclofenac can be approached by pseudo first-order kinetics and it followed the Langmuir-Hinshelwood model very well. The co-doped catalyst with 0.6% Mn and 1% Ce molar ratios appeared to be the most photoactive catalyst with 94% of DCF removal and an apparent rate constant of 0.012 min−1., Peer reviewed

The photodegradation of diclofenac from aqueous medium under UV-A light condition has been essayed using co-doped with manganese and silver TiO2 photocatalysts. X-ray diffraction, Raman spectroscopy, Scanning electron microscopy, Transmission electron microscopy, High resolution transmission electron microscopy, Energy dispersive X-ray, N2 adsorption-desorption measurements at 77 K, UV–Visible diffuse reflectance, X-ray photoelectron spectroscopy and photoluminescence analyses were used to characterize the materials. A high surface specific area of 165 m2/g, low band gap energy (2.7 eV) and effective charge separation were obtained for the 0.5%Ag-0.6%Mn/TiO2 photocatalyst. The results of the photocatalytic experiments showed that co-doping improved the photocatalytic activity of TiO2. In particular, TiO2 co-doped with 0.6 mol% Mn and 0.5 mol% Ag exhibited the maximum diclofenac removal (86%) after 4 h under UV-A light irradiation. The photodegradation rates followed a first order kinetics according to the Langmuir-Hinshelwood model, being the highest apparent rate of 0.0064 min−1. The photocatalytic performance appears as related to the specific surface area, the low optical band gap energy, the creation of surface oxygen vacancies and the efficient separation of photogenerated electron-hole pairs., Peer reviewed

Silicone microreactors containing microchannels of 500 μm width in a single or triple stack configuration have been manufactured, coated with an Au/TiO2 photocatalyst and tested for the photocatalytic production of hydrogen from water-ethanol gaseous mixtures under UV irradiation. Computational fluid dynamics (CFD) simulations have revealed that the design of the distributing headers allowed for a homogeneous distribution of the gaseous stream within the channels of the microreactors. A rate equation for the photocatalytic reaction has been developed from the experimental results obtained with the single stack operated under different ethanol partial pressures, light irradiation intensities and contact times. The hydrogen photoproduction rate has been expressed in terms of a Langmuir-Hinshelwood-type equation that accurately describes the process considering that hydrogen is produced through the dehydrogenation of ethanol to acetaldehyde. This equation incorporates an apparent rate constant (kapp) that has been found to be proportional to the intrinsic kinetic rate constant (k), and that depends on the light intensity (I) as follows: kapp = k·I0.65. A three-dimensional isothermal CFD model has been developed in which the previously obtained kinetic equation has been implemented. The model adequately describes the production of hydrogen of both the single and triple stacks. Moreover, the specific hydrogen productions (i.e. per gram of catalyst) are very close for both stacks thus suggesting that the scaling-up of the process could be accomplished by simply numbering-up. However, small deviations between the experimental and predicted hydrogen production suggest that a fraction of the radiation is absorbed by the microreactor components which should be taken into account for scaling-up purposes., This work has been funded through MINECO grants and FEDER funding ENE2015-63969-R and ENE2015-66975-C3-1-R. JL is Serra Húnter Fellow and is grateful to ICREA Academia program. AC is grateful to MINECO for PhD grant BES-2013-065709. LS is grateful to Generalitat de Catalunya for a Beatriu de Pinós grant (2013 BP-B 00007).