The effect of dissolved chlorides on the photocatalytic degradation properties of titania in wastewater treatment.

We investigate the effect of chlorides on the photocatalytic degradation of phenol by titania polymorphs (anatase and rutile). We demonstrate how solubilised chlorides can affect the hydroxyl radical formation on both polymorphs with an overall effect on their photodegradative activity. Initially, the photocatalytic activity of anatase and rutile for phenol degradation is investigated in both standard water and brines. With anatase, a significant reduction of the phenol conversion rate is observed (from a pseudo-first-order rate constant k = 5.3 × 10-3 min-1 to k = 3.5 × 10-3 min-1). In contrast, the presence of solubilised chlorides results in enhancement of rutile activity under the same reaction conditions (from 2.3 × 10-3 min-1 to 4.8 × 10-3 min-1). Periodic DFT methods are extensively employed and we show that after the generation of charge separation in the modelled titania systems, adsorbed chlorides are the preferential site for partial hole localisation, although small energy differences are computed between partially localised hole densities over adsorbed chloride or hydroxyl. Moreover, chlorides can reduce or inhibit the ability of r-TiO2 (110) and a-TiO2 (101) systems to localise polarons in the slab structure. These results indicate that both mechanisms - hole scavenging and the inhibition of hole localisation - can be the origin of the effect of chlorides on photocatalytic activity of both titania polymorphs. These results provide fundamental insight into the photocatalytic properties of titania polymorphs and elucidate the effect of adsorbed anions over radical formation and oxidative decomposition of organic pollutants.

Synthetic Naphthoquinone Derivatives as Anticancer Agents in Ovarian Cancer: Cytotoxicity Assay and Investigation of Possible Biological Mechanisms Action.

In this study, eight naphthoquinone derivatives were synthesized in yields ranging from 52 to 96% using easy, fast, and low-cost methodologies. All naphthoquinone derivatives were screened for their in vitro anti-proliferative activities against OVCA A2780 cancer cell lines. Amongst all analysed compounds, derivatives 3-5 presented the most prominent cytotoxic potential. Naphthoquinones 3 and 4, bearing sulfur-containing groups, were identified as having high potential for ROS production, in particular the superoxide anion. Furthermore, 3 and 4 compounds caused a decrease in the cell population in G0/G1 and induced more than 90% of the cell population to apoptosis. Compound 5 did not act in any of these processes. Finally, compounds 3-5 were tested for their inhibitory ability against PI3K and MAPK. Compounds 3 and 4 do not inhibit the PI3K enzyme. On the other hand, the naphthoquinone-polyphenol 5 was only able to inhibit the percentage of cells expressing pERK.

Cation-doping strategies for tuning of zirconia acid-base properties.

The role of Y-, Ca- and Ce-doping of cubic zirconia (c-ZrO2) (111) surface on its acidity, basicity and the interplay between surface acid-base pairs is investigated by computational methods. The most stable surface structures for this investigation were initially determined based on previous studies of Y-doped c-ZrO2 (111) and by a detailed exploration of the most stable configuration for Ca-doped c-ZrO2 (111) and Ce-doped c-ZrO2 (111). Next, surface mapping by basic probe molecules (NH3 and pyridine) revealed a general reduction of the acidity of the surface sites, although a few exceptions were observed for zirconium ions at next nearest neighbour (NNN) positions to the oxygen vacancy and at the nearest neighbour (NN) position to the dopants. Adsorption of CO2 over basic sites revealed a cooperative interplay between acid-base groups. In this case, the overall effect observed was the decrease of the calculated adsorption energies when compared with the pristine surface. Moreover, spontaneous formation of η 3-CO2 systems from initial η 2-CO2 configurations indicates a decrease in the required energy for forming oxygen vacancies in the doped ZrO2 systems at NNN positions or further away from the existing vacancy site.

Role of Sulfation of Zirconia Catalysts in Vapor Phase Ketonization of Acetic Acid.

The effect of the sulfation of zirconia catalysts on their structure, acidity/basicity, and catalytic activity/selectivity toward the ketonization of organic acids is investigated by a combined experimental and computational method. Here, we show that, upon sulfation, zirconia catalysts exhibit a significant increase in their Brønsted and Lewis acid strength, whereas their Lewis basicity is significantly reduced. Such changes in the interplay between acid-base sites result in an improvement of the selectivity toward the ketonization process, although the measured conversion rates show a significant drop. We report a detailed DFT investigation of the putative surface species on sulfated zirconia, including the possible formation of dimeric pyrosulfate (S2O7 2-) species. Our results show that the formation of such a dimeric system is an endothermic process, with energy barriers ranging between 60.0 and 70.0 kcal mol-1, and which is likely to occur only at high SO4 2- coverages (4 S/nm2), high temperatures, and dehydrating conditions. Conversely, the formation of monomeric species is expected at lower SO4 2- coverages, mild temperatures, and in the presence of water, which are the usual conditions experienced during the chemical upgrading of biofuels.

Hetero-Diels-Alder Reactions of Quinone Methides: The Origin of the α-Regioselectivity of 3-Methylene-1,2,4-naphthotriones.

The regioselective formation of α- and ß-lapachone via hetero-Diels-Alder reactions was investigated by experimental and computational approaches. The experimentally observed α-selectivity was explored in detail, revealing that the lower energy barrier for the formation of α-lapachone is a result of lower Pauli repulsion throughout the reaction path, when compared to the ß-isomer. By comparing equivalent points on both α- and ß-lapachone potential energy surfaces (PES), according to the activation strain model (ASM) and energy decomposition analysis (EDA), we were able to demonstrate that the Pauli repulsion term increases more significantly when going from reactants to TSß than to TSα, resulting in lower interaction energy in the early stages of the reaction path and in a later transition state for ß-lapachone. Moreover, we confirmed that regio- and diastereoselectivity trends previously reported for other quinone methide intermediates are also observed for 3-methylene-1,2,4-naphthotriones, such as small endo/exo diastereoselectivity, as well as pronounced ortho/meta regioselectivity for reactions performed with dienophile containing electron-releasing groups. The results presented here provide a deeper understanding of the reactivity of quinone methide derivatives, aiding the future rational design of the reaction condition, structural modification of possible quinone methide intermediates, and the development of more selective synthetic routes for quinone derivatives.

Modelling the bulk properties of ambient pressure polymorphs of zirconia.

We report a detailed survey of the calculated bulk properties of zirconia using GGA and meta-GGA functionals (PBE, PBEsol, RPBE, and TPSS), dispersion (Grimme's D2 and D3 approach), and on-site Coulomb repulsion correction (U = 2-8 eV). Structural, elastic, mechanical, and dielectric properties, as well as energetics, electronic structure, and phonon dispersion curves were computed and compared to previous investigations to identify the best DFT approach for a consistent in silico description of zirconia polymorphs. In general, inclusion of dispersion corrections led to only small changes in the calculated properties, whereas DFT+U (U = 2 or 4 eV) reduced the deviations of calculated properties from the experimental results, although deterioration of the structure and relative stabilities may be observed in some cases. Standard PBEsol, RPBE+U, and PBE+U were the best methodologies for a simultaneous description of the three polymorphs of ZrO2. RPBE+U, however, was the only functional to conserve the distinct structures and stabilities of c-, t-, and m-ZrO2 when U = 4 eV was used, resulting in the best in silico replication of the band gaps of ZrO2, whilst outperforming the other methodologies in the description of elastic, mechanical, and dielectric properties of this material. Overall, these results provide insight into the most appropriate DFT methodology for in silico investigations of ZrO2, and show that simultaneous description of all three ambient pressure zirconia polymorphs by DFT techniques with acceptable levels of accuracy can be achieved only when the correct choice of methodology is applied.

α- and ß-Lapachone Isomerization in Acidic Media: Insights from Experimental and Implicit/Explicit Solvation Approaches.

Combined experimental and mixed implicit/explicit solvation approaches were employed to gain insights into the origin of switchable regioselectivity of acid-catalyzed lapachol cyclization and α-/ß-lapachone isomerization. It was found that solvating species under distinct experimental conditions stabilized α- and ß-lapachone differently, thus altering the identity of the thermodynamic product. The energy profile for lapachol cyclization revealed that this process can occur with low free-energy barriers (lower than 8.0 kcal mol-1 ). For α/ß isomerization in a dilute medium, the computed enthalpic barriers are 15.1 kcal mol-1 (α→ß) and 14.2 kcal mol-1 (ß→α). These barriers are lowered in concentrated medium to 11.5 and 12.6 kcal mol-1 , respectively. Experimental determination of isomers ratio was quantified by HPLC and NMR measurements. These findings provide insights into the chemical behavior of lapachol and lapachone derivatives in more complex environments.

Mechanism of the Catalytic Carboxylation of Alkylboronates with CO2 Using Ni-NHC Complexes: A DFT Study.

A new mechanism is proposed for the Ni-catalyzed carboxylation of organoboronates with CO2 . DFT investigations at the PBE0-D3 level have shown that direct CO2 addition to the catalysts [Ni(NHC)(Allyl)Cl] (1NHC , NHC=IMe, IPr, SIPr and IPr*) is kinetically disfavored and formation of the Aresta-type intermediate is unlikely to occur. According to the mechanism proposed here, the carboxylation process starts with addition of the borate species to 1NHC , followed by transmetalation, CO2 cycloaddition and carboxylation. The rate-determining step was identified as being the transmetalation process, with computed relative free energy barriers of 34.8, 36.8, and 33.5 kcal mol-1 for 1IPr , 1SIPr and 1IPr* , respectively.

Insight into and Computational Studies of the Selective Synthesis of 6H-Dibenzo[b,h]xanthenes.

Starting from 2-hydroxy-1,4-naphthoquinone (lawsone), we synthesized eight new 6H-dibenzo[b,h]xanthene derivatives selectively under solvent-free conditions. Spectroscopic investigations confirmed that only the isomer 6H-dibenzo[b,h]xanthene was obtained in all eight cases. Computational studies provide a rationalization for the selective appearance of these isomers having as an intermediate an addition product.