Defect chemistry and transport properties of BaxCe0.85M0.15O3-d

The site-incorporation mechanism of M3+ dopants into A2+B4+O3 perovskites controls the overall defect chemistry and thus their transport properties. For charge-balance reasons, incorporation onto the A2+-site would require the creation of negatively charged point defects (such as cation vacancies), whereas incorporation onto the B4+-site is accompanied by the generation of positively charged defects, typically oxygen vacancies. Oxygen-vacancy content, in turn, is relevant to proton-conducting oxides in which protons are introduced via the dissolution of hydroxyl ions at vacant oxygen sites. We propose here, on the basis of x-ray powder diffraction studies, electron microscopy, chemical analysis, thermal gravimetric analysis, and alternating current impedance spectroscopy, that nominally B-site doped barium cerate can exhibit dopant partitioning as a consequence of barium evaporation at elevated temperatures. Such partitioning and the presence of significant dopant concentrations on the A-site negatively impact proton conductivity. Specific materials examined are BaxCe0.85M0.15O3-d (x = 0.85 - 1.20; M = Nd, Gd, Yb). The compositional limits for the maximum A-site incorporation are experimentally determined to be: (Ba0.919Nd0.081)(Ce0.919Nd0.081)O3, (Ba0.974Gd0.026)(Ce0.872Gd0.128)O2.875, and Ba(Ce0.85Yb0.15)O2.925. As a consequence of the greater ability of larger cations to exist on the Ba site, the H2O adsorption and proton conductivities of large-cation doped barium cerates are lower than those of small-cation doped analogs

Unveiling interactions between DNA and cytotoxic 2-arylpiperidinyl-1,4-naphthoquinone derivatives: A combined electrochemical and computational study

Indexación: Scopus.Three 2-arylpiperidinyl-1,4-naphthoquinone derivatives were synthesized and evaluated in vitro to determine their cytotoxicity on cancer and normal cell lines. In order to establish their possible action mechanism, the electrochemical behaviour of these quinones was examined using cyclic voltammetry (CV) as technique by using a three-electrode setup: a glassy carbon, Ag/AgCl (in 3 M KCl), and platinum wire as working, reference, and counter electrodes, respectively. Kinetic studies were done to determine the control of the reduction reaction and the number of transferred electrons in the process. Furthermore, the addition of dsDNA to the quinone solutions allowed for the observation of an interaction between each quinone and dsDNA as the current-peaks became lower in presence of dsDNA. Otherwise, motivated to support the aforementioned results, electronic structure calculations at the TPSS-D3/6-31+G(d,p) level of theory were carried out in order to find the most favourable noncovalently bonded complexes between quinones and DNA. Noncovalent complexes formed between DNA and 2-arylpiperidinyl-1,4-naphthoquinones and stabilized by π-stacking interactions along with the well-known hydrogen-bonded complexes were found, with the former being more stable than the latter. These results suggest that the intercalation of these quinone derivatives in DNA is the most likely action mechanism. © 2018 King Saud Universityhttps://www.sciencedirect.com/science/article/pii/S1878535218300893?via%3Dihu

Unraveling public good games

This paper provides experimental evidence on how players predict end-game effects in a linear public good game. Our regression analysis yields a measure of the relative importance of priors and signals on subjects’ beliefs on contributions and allows us to conclude that, first, the weight of the signal is relatively unimportant, while priors have a large weight and, second, priors are the same for all periods. Hence, subjects do not expect end-game effects and there is very little updating of beliefs. We argue that the sustainability of cooperation is related to this pattern of belief formation

Homoerotic Medievalism: Looking at Queer Desire in the Homosocial Relationships of Chaucer’s “The Knight’s Tale” and Fletcher and Shakespeare’s The Two Noble Kinsmen

The purpose of this thesis is to explore queer interiority within the heteronormative social constructions of late medieval England. Queer interiority is not an occurrence of modernity, but rather a response to social constructions that date back to the Middle Ages. It is essential to account for queerness in the Middle Ages because authors like Chaucer promote the successive resurfacing of queer characters within heteronormative social constructions. Writing during the queer reign of Richard II, Chaucer constructs the interior identities of Palamon and Arcite as a reflection of the king and the political norms of England. Inspired by Chaucer, authors in the early modern period, such as Fletcher and Shakespeare, explore the queer propositions of Chaucer and reimagine his stories by extending the characters’ queer potential. This phenomenon is known as medievalism, which encompasses the transformations and retellings of medieval cultural productions in post-medieval periods. Queerness in medieval and early modern literature occurs through desire, nominally, same-sex relationships; it exists in the mimicked normative relationship constructions of same-sex characters. To access queer desire, Lacanian psychoanalysis explains the signification of language in romantic discourse. His theories do not apply solely to heterosexual relationships, but also the “inversions” (as Freud would name it) that exist when two characters of the same sex desire one another. Through close readings of Geoffrey Chaucer\u27s “The Knight\u27s Tale” and John Fletcher and William Shakespeare\u27s The Two Noble Kinsmen, as well as historical, psychoanalytic, theoretical, and analytical texts, this paper will account for queerness in medievalism

On the Naturalness of Higgs Inflation

We critically examine the recent claim that the Standard Model Higgs boson ${\cal H}$ could drive inflation in agreement with observations if $|{\cal H}|^2$ has a strong coupling $\xi\sim 10^4$ to the Ricci curvature scalar. We first show that the effective theory approach upon which that claim is based ceases to be valid beyond a cutoff scale $\Lambda=m_p/\xi$, where $m_p$ is the reduced Planck mass. We then argue that knowing the Higgs potential profile for the field values relevant for inflation ($|{\cal H}|>m_p/\sqrt{\xi}\gg \Lambda$) requires knowledge of the ultraviolet completion of the SM beyond $\Lambda$. In absence of such microscopic theory, the extrapolation of the pure SM potential beyond $\Lambda$ is unwarranted and the scenario is akin to other ad-hoc inflaton potentials afflicted with significant fine-tuning. The appealing naturalness of this minimal proposal is therefore lost.Comment: 9 pages. Replaced with published version, plus a footnote clarifying the use of power counting estimate

The method of Gaussian weighted trajectories. V. On the 1GB procedure for polyatomic processes

In recent years, many chemical reactions have been studied by means of the quasi-classical trajectory (QCT) method within the Gaussian binning (GB) procedure. The latter consists in "quantizing" the final vibrational actions in Bohr spirit by putting strong emphasis on the trajectories reaching the products with vibrational actions close to integer values. A major drawback of this procedure is that if N is the number of product vibrational modes, the amount of trajectories necessary to converge the calculations is ~ 10^N larger than with the standard QCT method. Applying it to polyatomic processes is thus problematic. In a recent paper, however, Czako and Bowman propose to quantize the total vibrational energy instead of the vibrational actions [G. Czako and J. M. Bowman, J. Chem. Phys., 131, 244302 (2009)], a procedure called 1GB here. The calculations are then only ~ 10 times more time-consuming than with the standard QCT method, allowing thereby for considerable numerical saving. In this paper, we propose some theoretical arguments supporting the 1GB procedure and check its validity on model test cases as well as the prototype four-atom reaction OH+D_2 -> HOD+D

Identities among relations for higher-dimensional rewriting systems

We generalize the notion of identities among relations, well known for presentations of groups, to presentations of n-categories by polygraphs. To each polygraph, we associate a track n-category, generalizing the notion of crossed module for groups, in order to define the natural system of identities among relations. We relate the facts that this natural system is finitely generated and that the polygraph has finite derivation type.Comment: 16 pages, corrected version after review, to appear in S\'eminaires et Congr\`e