Influence of the aspect ratio on boiling flows in rectangular mini-channels

This article presents experiments conducted with two single rectangular mini-channels of same hydraulic diameter (1.4 mm) and different aspect ratios for conditions of horizontal boiling flow. The Forane® 365 HX used was subcooled (ΔT_sub = 15 °C) for all the boiling curves presented in the paper. Local heat transfer coefficients were measured for heat flux ranging from 25 to 62 kW m⁻² and mass flux from 200 kg m⁻² s⁻¹ to 400 kg m⁻² s⁻¹. The boiling flows were observed with two different cameras (depending on the flow velocity) through a visualization window. The flow patterns in the two channels were compared for similar conditions. The results show that the boiling heat transfer coefficient and the pressure drop values are different for the two single mini-channels. For low heat flux condition, the channel with lowest aspect ratio (H/W = 0.143) has a higher heat transfer coefficient. On the other hand, for high heat flux condition, the opposite situation occurs, namely the heat transfer coefficient becomes higher for the channel with highest aspect ratio (H/W = 0.43). This is probably due to the earlier onset of dryout in the channel with lowest aspect ratio. For the two cases of heating, the pressure drop for the two-phase flow remains lower for the channel with lowest aspect ratio. These results show that the aspect ratio plays a substantial role for boiling flows in rectangular channels. As for single-phase flows, the heat transfer characteristics are significantly influenced (even though the hydraulic diameter remains the same) by this parameter.     

Regio et stereochimie de la reduction de derives d'alcools propargyliques catalysee par un complexe de palladium (O)

Regio and stereoselectivity of the palladium catalyzed reduction of propargylic halides and esters is greatly influenced by the nature of the hydride donor as by the leaving group. Best results in allene formation are observed in the reduction by lithium triethyl-borohydride of mesylates and phosphates. In the former case, reaction occurs with anti displacement of the sulfonyl group.     

Effondrement de quotients aléatoires de groupes hyperboliques avec torsion

We show that random quotients of hyperbolic groups with ‘harmful’ torsion collapse at densities smaller than expected. To cite this article: Y. Ollivier, C. R. Acad. Sci. Paris, Ser. I 341 (2005).     

Conformational arm-wrestling: battles for stereochemical control in benzamides bearing matched and mismatched chiral 2- and 6-substituents

The orientation of a tertiary amide group adjacent to an aromatic ring may be governed by the stereochemistry of an adjacent chiral substituent. With a chiral substituent in both ortho positions, matched/mismatched pairs of isomers result. Evidence for matched stereochemistry is provided by the clean NMR spectra of single conformers, while mismatching gives poor or unexpected selectivities in the formation of chiral substituents, or mixtures of amide conformers. Attempts to use the match-mismatch effect to select for racemic pairs of enantiomeric substituents, and hence develop a "racemate-sequestering" reagent, are described, along with the use of "matching" to scavenge a single enantiomer of a diamine from material of incomplete enantiomeric purity.     

An integrable example of gradient flow based on optimal transport of differential forms

Optimal transport theory has been a powerful tool for the analysis of parabolic equations viewed as gradient flows of volume forms (or, in other words, 0-currents) according to suitable transportation metrics. In this paper, we present an example of gradient flow for closed \((d-1)\)-differential forms, or, more appropriately, to closed 1-currents, which can be identified to divergence-free vector fields, in the Euclidean space \(\mathbb {R}^d\). In spite of its apparent complexity, the resulting very degenerate parabolic system is fully integrable and can be viewed, in a suitable sense, as an Eulerian version of the heat equation for loops in the Euclidean space. We analyze this system in terms of “relative entropy” and “dissipative solutions” and provide global existence and weak–strong uniqueness results.     

X-ray absorption study of Cu,Zn SOD under high pressure

Abstract

We have investigated Cu, Zn Superoxide Dismutase (Cu, Zn SOD) metal sites at high pressure using X-ray absorption. XAS (X-ray Absorption Spectroscopy) gives information on local structure and it is particularly suited to metal site investigation. To the best of our knowledge, this is the first time that protein conformational states have been investigated using the high pressure XAS technique. Cu, Zn SOD catalyses the dismutation of toxic oxygen radicals produced in cells; this reaction occurs at the copper metal site. Structural changes around the copper, induced by pressure, can be directly related to protein substates. Their characterisation is thus important in the understanding of protein activity.

The high-pressure device was a Paris-Edinburgh large volume cell.

Experiments were performed on lyophilised Cu, Zn SOD between 0 and 48 kbar at the copper and zinc K-edges. The two metal local atomic environments have a different behaviour as pressure increases: copper exhibits a more flexible environment; on the contrary, zinc shows small structural modifications. We have identified a state, formed between 3 and 8 kbar, which is stable up to 48 kbar.     

An algorithm to identify automorphisms which arise from self-induced interval exchange transformations

We give an algorithm to determine if the dynamical system generated by a positive automorphism of the free group can also be generated by a self-induced interval exchange transformation. The algorithm effectively yields the interval exchange transformation in case of success.     

Exploring the latent segmentation space for the assessment of multiple change-point models

This paper addresses the retrospective or off-line multiple change-point detection problem. Multiple change-point models are here viewed as latent structure models and the focus is on inference concerning the latent segmentation space. Methods for exploring the space of possible segmentations of a sequence for a fixed number of change points may be divided into two categories: (i) enumeration of segmentations, (ii) summary of the possible segmentations in change-point or segment profiles. Concerning the first category, a dynamic programming algorithm for computing the top $N$ most probable segmentations is derived. Concerning the second category, a forward-backward dynamic programming algorithm and a smoothing-type forward-backward algorithm for computing two types of change-point and segment profiles are derived. The proposed methods are mainly useful for exploring the segmentation space for successive numbers of change points and provide a set of assessment tools for multiple change-point models that can be applied both in a non-Bayesian and a Bayesian framework. We show using examples that the proposed methods may help to compare alternative multiple change-point models (e.g. Gaussian model with piecewise constant variances or global variance), predict supplementary change points, highlight overestimation of the number of change points and summarize the uncertainty concerning the position of change points.     

DABCOnium: An Efficient and High‐Voltage Stable Singlet Oxygen Quencher for Metal–O2 Cells

Singlet oxygen (¹O₂) causes a major fraction of the parasitic chemistry during the cycling of non‐aqueous alkali metal‐O₂ batteries and also contributes to interfacial reactivity of transition‐metal oxide intercalation compounds. We introduce DABCOnium, the mono alkylated form of 1,4‐diazabicyclo[2.2.2]octane (DABCO), as an efficient ¹O₂ quencher with an unusually high oxidative stability of ca. 4.2 V vs. Li/Li⁺. Previous quenchers are strongly Lewis basic amines with too low oxidative stability. DABCOnium is an ionic liquid, non‐volatile, highly soluble in the electrolyte, stable against superoxide and peroxide, and compatible with lithium metal. The electrochemical stability covers the required range for metal–O₂ batteries and greatly reduces ¹O₂ related parasitic chemistry as demonstrated for the Li–O₂ cell.     

Self-Assembly and Fluorescence of Tetracationic Liquid Crystalline Tetraphenylethene

A series of tetraguanidinium tetraphenylethene (TPE) arylsulfonates with different chain lengths was prepared via ionic self-assembly of tetraguanidinium TPE chloride and the respective methyl arylsulfonates. Liquid crystalline properties were studied by differential scanning calorimetry, polarizing optical microscopy and X-ray diffraction. Tetraguanidinium TPE arylsulfonates with chain lengths of C₈–C₁₂ displayed hexagonal columnar mesophases over a broad temperature range, while derivatives with longer chains showed oblique columnar phases. In solution all compounds displayed aggregation-induced emission behaviour. Temperature-dependent luminescence spectra of the bulk phase of the tetraguanidinium TPE arylsulfonate with C₁₄ side chains revealed a strong luminescence both in the solid state and the oblique columnar mesophase. The emission behaviour was rationalized by a unique combination of restriction of intramolecular rotation of the TPE core, Coulomb interaction between the guanidinium cations and π–π interactions of the anionic arylsulfonate moieties.