High‐Yield Formation of Substituted Tetracyanobutadienes from Reaction of Ynamides with Tetracyanoethylene

A high‐yielding sequence of [2+2] cycloaddition–retroelectrocyclization of ynamides with tetracyanoethylene (TCNE) is described. The reaction provided tetracyanobutadiene (TCBD) species, which were characterized by various techniques. DFT and TD‐DFT calculations were also performed to complement experimental findings.     

Selective and Wash-Resistant Fluorescent Dihydrocodeinone Derivatives Allow Single-Molecule Imaging of μ-Opioid Receptor Dimerization

μ-Opioid receptors (μ-ORs) play a critical role in the modulation of pain and mediate the effects of the most powerful analgesic drugs. Despite extensive efforts, it remains insufficiently understood how μ-ORs produce specific effects in living cells. We developed new fluorescent ligands based on the μ-OR antagonist E-p-nitrocinnamoylamino-dihydrocodeinone (CACO), that display high affinity, long residence time and pronounced selectivity. Using these ligands, we achieved single-molecule imaging of μ-ORs on the surface of living cells at physiological expression levels. Our results reveal a high heterogeneity in the diffusion of μ-ORs, with a relevant immobile fraction. Using a pair of fluorescent ligands of different color, we provide evidence that μ-ORs interact with each other to form short-lived homodimers on the plasma membrane. This approach provides a new strategy to investigate μ-OR pharmacology at single-molecule level.     

The Relationship Between Stock Markets Of Major Developed Countries And Asian Emerging Markets

With the emergence of new capital markets and liberalization of stock markets in recent years, there has been an increase in investors' interest in international diversification. This is so because international diversification allows investors to have a larger basket of foreign securities to choose from as part of their portfolio assets, so as to enhance the reward-to-volatility ratio. This benefit would be limited if national equity markets tend to move together in the long run. This paper thus studies the issue of co-movement between stock markets in major developed countries and those in Asian emerging markets using the concept of cointegration. We find that there is co-movement between some of the developed and emerging markets, but some emerging markets do differ from the developed markets with which they share a long-run equilibrium relationship. Furthermore, it has been observed that there has been increasing interdependence between most of the developed and emerging markets since the 1987 Stock Market Crash. This interdependence intensified after the 1997 Asian Financial Crisis. With this phenomenon of increasing co-movement between developed and emerging stock markets, the benefits of international diversification become limited.     

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.     

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.     

Effect of Metal Vapours on the Radiation Properties of Thermal Plasmas

In metallurgic applications of thermal plasmas the presence of metal vapour, even in small proportion tends to increase the electron number density and to modify some basic properties such as the electrical conductivity and the radiation emission. In this paper we focus on the influence of these vapours on the radiation properties. After the definition of some necessary and basic functions and laws we briefly present the mechanisms responsible for emission and absorption of radiation in thermal plasmas. Then an important section is devoted to the role of metal vapours on the net emission coefficient which is the most popular parameter used to evaluate the radiation power losses in general models. It is shown that metal vapours increase the emission especially at low and intermediate temperatures (T < 12,000 K) and that their relative influence depends on the nature of the initial gas and of the metal itself. We list a rather important number of references presenting calculation of net emission in various gas–metal mixtures. Finally we show in a last section the influence of metal radiation on general plasma properties such as the energy transfer (other methods than the net emission coefficient), the cooling effect, the global energy balance and the heating of particulates injected in the plasma. The most spectacular effects are the increase of radiation losses in the energy balance and the complex role of the metal in the local cooling of the plasma.     

Optical Radiation Associated with Photobiological Hazards for Argon GTAW Arcs

Plasma Chemistry and Plasma Processing - Gas tungsten arc welding (GTAW), a widely used industrial process, is one of the most intense artificial sources of optical radiation. This paper presents a...     

Approximation by Algebraic Integers and Hausdorff Dimension

The paper computes the Hausdorff dimension of sets of real numberswhich are close to infinitely many real algebraic integers ofbounded degree. It also investigates the distribution of realalgebraic integers of bounded degree, which are proved to beevenly spaced.     

Organic cross-linked electropolymers as supported oxidation catalysts: poly((tetrakis(9,9'-spirobifluorenyl)porphyrin)manganese) films

Anodic oxidation of free base and manganese complexes of tetraspirobifluorenylporphyrins leads to the coating of the working electrode by insoluble electroactive poly(9,9'-spirobifluorene-free and manganese porphyrin) films which electrochemical behavior and physicochemical properties are described. After removal from the electrode, the manganese-complexed polymers were evaluated as catalysts for the oxidation of alkenes by iodobenzene diacetate or iodosylbenzene. The results show that the reactions proceeded very efficiently at room temperature with good yields. The electrosynthesized polymer catalysts can be recycled by simple filtration and reused even up to the eighth cycle without loss of activity and selectivity. These results represent an important improvement over those previously described for manganese-porphyrin-catalyzed epoxidation reactions.     

Sharp phase transition theorems for hyperbolicity of random groups

We prove that in various natural models of a random quotient of a group, depending on a density parameter, for each hyperbolic group there is some critical density under which a random quotient is still hyperbolic with high probability, whereas above this critical value a random quotient is very probably trivial. We give explicit characterizations of these critical densities for the various models.