71 resultados para binary and ternary electrocatalysts
Resumo:
In a development from material introduced in recent work, we discuss the interconnections between ternary rings of operators (TROs) and right C*-algebras generated by JC*-triples, deducing that every JC*-triple possesses a largest universally reversible ideal, that the universal TRO commutes with appropriate tensor products and establishing a reversibility criterion for type I JW*-triples.
Resumo:
We embark upon a systematic investigation of operator space structure of JC*-triples via a study of the TROs (ternary rings of operators) they generate. Our approach is to introduce and develop a variety of universal objects, including universal TROs, by which means we are able to describe all possible operator space structures of a JC*-triple. Via the concept of reversibility we obtain characterisations of universal TROs over a wide range of examples. We apply our results to obtain explicit descriptions of operator space structures of Cartan factors regardless of dimension
Resumo:
Scoring rules are an important tool for evaluating the performance of probabilistic forecasting schemes. A scoring rule is called strictly proper if its expectation is optimal if and only if the forecast probability represents the true distribution of the target. In the binary case, strictly proper scoring rules allow for a decomposition into terms related to the resolution and the reliability of a forecast. This fact is particularly well known for the Brier Score. In this article, this result is extended to forecasts for finite-valued targets. Both resolution and reliability are shown to have a positive effect on the score. It is demonstrated that resolution and reliability are directly related to forecast attributes that are desirable on grounds independent of the notion of scores. This finding can be considered an epistemological justification of measuring forecast quality by proper scoring rules. A link is provided to the original work of DeGroot and Fienberg, extending their concepts of sufficiency and refinement. The relation to the conjectured sharpness principle of Gneiting, et al., is elucidated.
Resumo:
Lorenz’s theory of available p otential energy (APE) remains the main framework for studying the atmospheric and oceanic energy cycles. Because the APE generation rate is the volume integral of a thermodynamic efficiency times the local diabatic heating/cooling rate, APE theory is often regarded as an extension of the theory of heat engines. Available energetics in classical thermodynamics, however, usually relies on the concept of exergy, and is usually measured relative to a reference state maximising entropy at constant energy, whereas APE’s reference state minimises p otential energy at constant entropy. This review seeks to shed light on the two concepts; it covers local formulations of available energetics, alternative views of the dynamics/thermodynamics coupling, APE theory and the second law, APE production/dissipation, extensions to binary fluids, mean/eddy decomp ositions, APE in incompressible fluids, APE and irreversible turbulent mixing, and the role of mechanical forcing on APE production.
Resumo:
The author contends that many of the conventions of Italian film studies derive from the conflicts and the critical vocabulary that shaped the Italian reception of neorealism in the first decade after the Second World War. Those conflicts, and that critical vocabulary, which lie at the foundation of what has been called the ‘institution of neorealism,’ established an irreconcilable binary: Cronaca and Narrativa. For the neorealists and their critics, Cronaca stood for the effort to record data faithfully, while Narrativa represented the effort to employ the shaping force of human invention in the representation of information. This essay’s first section analyzes the earliest reviews of Rossellini’s Roma città aperta alongside the contemporaneous literary debates over Cronaca and Narrativa. The second section reconsiders the reception of Pratolini’s Metello and Visconti’s Senso, which similarly centered upon the conflict between Cronaca and Narrativa. The third section proposes that the concepts which have often been employed to unify neorealism are destabilized by the Cronaca/Narrativa binary. In search of a solution to neorealism’s conceptual instability, this essay proposes more critical and purposeful appropriations of the movement’s problematic genealogy.
Resumo:
Binary mixed-metal variants of the one-dimensional MCN compounds (M = Cu, Ag, and Au) have been prepared and characterized using powder X-ray diffraction, vibrational spectroscopy, and total neutron diffraction. A solid solution with the AgCN structure exists in the (CuxAg1–x)CN system over the range (0 ≤ x ≤ 1). Line phases with compositions (Cu1/2Au1/2)CN, (Cu7/12Au5/12)CN, (Cu2/3Au1/3)CN, and (Ag1/2Au1/2)CN, all of which have the AuCN structure, are found in the gold-containing systems. Infrared and Raman spectroscopies show that complete ordering of the type [M–C≡N–M′–N≡C−]n occurs only in (Cu1/2Au1/2)CN and (Ag1/2Au1/2)CN. The sense of the cyanide bonding was determined by total neutron diffraction to be [Ag–NC–Au–CN−]n in (Ag1/2Au1/2)CN and [Cu–NC–Au–CN−]n in (Cu1/2Au1/2)CN. In contrast, in (Cu0.50Ag0.50)CN, metal ordering is incomplete, and strict alternation of metals does not occur. However, there is a distinct preference (85%) for the N end of the cyanide ligand to be bonded to copper and for Ag–CN–Cu links to predominate. Contrary to expectation, aurophilic bonding does not appear to be the controlling factor which leads to (Cu1/2Au1/2)CN and (Ag1/2Au1/2)CN adopting the AuCN structure. The diffuse reflectance, photoluminescence, and 1-D negative thermal expansion (NTE) behaviors of all three systems are reported and compared with those of the parent cyanide compounds. The photophysical properties are strongly influenced both by the composition of the individual chains and by how such chains pack together. The NTE behavior is also controlled by structure type: the gold-containing mixed-metal cyanides with the AuCN structure show the smallest contraction along the chain length on heating.
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Bis(o-hydroxyacetophenone)nickel(II) dihydrate, on reaction with 1,3-pentanediamine, yields a bis-chelate complex [NiL2]·2H2O (1) of mono-condensed tridentate Schiff baseligand HL {2-[1-(3-aminopentylimino)ethyl]phenol}. The Schiff base has been freed from the complex by precipitating the NiII as a dimethylglyoximato complex. HL reacts smoothly with Ni(SCN)2·4H2O furnishing the complex [NiL(NCS)] (2) and with CuCl2·2H2O in the presence of NaN3 or NH4SCN producing [CuL(N3)]2 (3) or [CuL(NCS)] (4). On the other hand, upon reaction with Cu(ClO4)2·6H2O and Cu(NO3)2·3H2O, the Schiff base undergoes hydrolysis to yield ternary complexes [Cu(hap)(pn)(H2O)]ClO4 (5) and [Cu(hap)(pn)(H2O)]NO3 (6), respectively (Hhap = o-hydroxyacetophenone and pn = 1,3-pentanediamine). The ligand HL undergoes hydrolysis also on reaction with Ni(ClO4)2·6H2O or Ni(NO3)2·6H2O to yield [Ni(hap)2] (7). The structures of the complexes 2, 3, 5, 6, and 7 have been confirmed by single-crystal X-ray analysis. In complex 2, NiII possesses square-planar geometry, being coordinated by the tridentate mono-negative Schiff base, L and the isothiocyanate group. The coordination environment around CuII in complex 3 is very similar to that in complex 2 but here two units are joined together by end-on, axial-equatorial azide bridges to result in a dimer in which the geometry around CuII is square pyramidal. In both 5 and 6, the CuII atoms display the square-pyramidal environment; the equatorial sites being coordinated by the two amine groups of 1,3-pentanediamine and two oxygen atoms of o-hydroxyacetophenone. The axial site is coordinated by a water molecule. Complex 7 is a square-planar complex with the Ni atom bonded to four oxygen atoms from two hap moieties. The mononuclear units of 2 and dinuclear units of 3 are linked by strong hydrogen bonds to form a one-dimensional network. The mononuclear units of 5 and 6 are joined together to form a dimer by very strong hydrogen bonds through the coordinated water molecule. These dimers are further involved in hydrogen bonding with the respective counteranions to form 2-D net-like open frameworks.
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The self-assembly in water of designed peptide amphiphile (PA) C16-ETTES containing two anionic residues and its mixtures with C16-KTTKS containing two cationic residues has been investigated. Multiple spectroscopy, microscopy, and scattering techniques are used to examine ordering extending from the β-sheet structures up to the fibrillar aggregate structure. The peptide amphiphiles both comprise a hexadecyl alkyl chain and a charged pentapeptide headgroup containing two charged residues. For C16-ETTES, the critical aggregation concentration was determined by fluorescence experiments. FTIR and CD spectroscopy were used to examine β-sheet formation. TEM revealed highly extended tape nanostructures with some striped regions corresponding to bilayer structures viewed edge-on. Small-angle X-ray scattering showed a main 5.3 nm bilayer spacing along with a 3 nm spacing. These spacings are assigned respectively to predominant hydrated bilayers and a fraction of dehydrated bilayers. Signs of cooperative self-assembly are observed in the mixtures, including reduced bundling of peptide amphiphile aggregates (extended tape structures) and enhanced β-sheet formation.
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This paper considers ways that experimental design can affect judgments about informally presented context shifting experiments. Reasons are given to think that judgments about informal context shifting experiments are affected by an exclusive reliance on binary truth value judgments and by experimenter bias. Exclusive reliance on binary truth value judgments may produce experimental artifacts by obscuring important differences of degree between the phenomena being investigated. Experimenter bias is an effect generated when, for example, experimenters disclose (even unconsciously) their own beliefs about the outcome of an experiment. Eliminating experimenter bias from context shifting experiments makes it far less obvious what the “intuitive” responses to those experiments are. After it is shown how those different kinds of bias can affect judgments about informal context shifting experiments, those experiments are revised to control for those forms of bias. The upshot of these investigations is that participants in the contextualist debate who employ informal experiments should pay just as much attention to the design of their experiments as those who employ more formal experimental techniques if they want to avoid obscuring the phenomena they aim to uncover
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As the calibration and evaluation of flood inundation models are a prerequisite for their successful application, there is a clear need to ensure that the performance measures that quantify how well models match the available observations are fit for purpose. This paper evaluates the binary pattern performance measures that are frequently used to compare flood inundation models with observations of flood extent. This evaluation considers whether these measures are able to calibrate and evaluate model predictions in a credible and consistent way, i.e. identifying the underlying model behaviour for a number of different purposes such as comparing models of floods of different magnitudes or on different catchments. Through theoretical examples, it is shown that the binary pattern measures are not consistent for floods of different sizes, such that for the same vertical error in water level, a model of a flood of large magnitude appears to perform better than a model of a smaller magnitude flood. Further, the commonly used Critical Success Index (usually referred to as F<2 >) is biased in favour of overprediction of the flood extent, and is also biased towards correctly predicting areas of the domain with smaller topographic gradients. Consequently, it is recommended that future studies consider carefully the implications of reporting conclusions using these performance measures. Additionally, future research should consider whether a more robust and consistent analysis could be achieved by using elevation comparison methods instead.
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This chapter looks at three films whose Portuguese urban settings offer a privileged ground for the re-evaluation of the classical-modern-postmodern categorisation with regard to cinema. They are The State of Things (Wim Wenders, 1982), Foreign Land (Walter Salles and Daniela Thomas, 1995) and Mysteries of Lisbon (Raúl Ruiz, 2010). In them, the city is the place where characters lose their bearings, names, identities, and where vicious circles, mirrors, replicas and mise-en-abyme bring the vertiginous movement that had characterised the modernist city of 1920s cinema to a halt. Curiously, too, it is the place where so-called postmodern aesthetics finally finds an ideal home in self-ironical tales that expose the film medium’s narrative shortcomings. Intermedial devices, whether Polaroid stills or a cardboard cut-out theatre, are then resorted to in order to turn a larger-than-life reality into framed, manageable narrative miniatures. The scaled-down real, however, turns out to be a disappointing simulacrum, a memory ersatz that unveils the illusory character of cosmopolitan teleology. In my approach, I start by examining the intertwined and transnational genesis of these films that resulted in three correlated visions of the end of history and of storytelling, typical of postmodern aesthetics. I move on to consider intermedia miniaturism as an attempt to stop time within movement, an equation that inevitably brings to mind the Deleuzian movement-time binary, which I revisit in an attempt to disentangle it from the classical-modern opposition. I conclude by proposing reflexive stasis and scale reversal as the common denominator across all modern projects, hence, perhaps, a more advantageous model than modernity to signify artistic and political values.
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Consideration of the geometrical features of the functional groups present in furosemide has enabled synthesis of a series of ternary co-crystals with predictable structural features, containing a robust asymmetric two-dimensional network.