On the density of 2‐colorable 3‐graphs in which any four points span at most two edges

Let ex₂(n, K) be the maximum number of edges in a 2‐colorable K‐free 3‐graph (where K={123, 124, 134} ). The 2‐chromatic Turán density of K is $\pi_{2}({K}_{4}^-) =lim_{{n}\to \infty} {ex}_{2}({n}, {K}_{4}^-)/\left(_{3}^{n}\right)Let ex₂(n, K) be the maximum number of edges in a 2‐colorable K‐free 3‐graph (where K={123, 124, 134} ). The 2‐chromatic Turán density of K is $\pi_{2}({K}_{4}^-) =lim_{{n}\to \infty} {ex}_{2}({n}, {K}_{4}^-)/\left(_{3}^{n}\right)$. We improve the previously best known lower and upper bounds of 0.25682 and 3/10?ε, respectively, by showing that This implies the following new upper bound for the Turán density of K In order to establish these results we use a combination of the properties of computer‐generated extremal 3‐graphs for small n and an argument based on “super‐saturation”. Our computer results determine the exact values of ex(n, K) for n≤19 and ex₂(n, K) for n≤17, as well as the sets of extremal 3‐graphs for those n. © 2009 Wiley Periodicals, Inc. J Combin Designs 18: 105–114, 2010     

Thermal performance investigation of DQW GaInNAs laser diodes

In this work, we optimize the thermal performance of a double quantum well GaInNAs ridge waveguide laser using an accurate in-house 2D electro-opto-thermal laser simulator. The simulator has shown good agreement with experiments after a detailed calibration procedure. Using calibrated material parameters, we investigate the influence of the cladding doping level on the heat generation within the laser. It is found that due to the competition between Joule heating and free carrier absorption, an optimum cladding doping level exists.     

Straightforward α‐Amino Nitrile Synthesis Through Mo(CO)6‐Catalyzed Reductive Functionalization of Carboxamides

The selective reduction of amides into an intermediate hemiaminal catalyzed by Mo(CO)₆ together with the inexpensive and easy to handle TMDS (1,1,3,3‐tetramethyldisiloxane) as reducing agent, followed by subsequent trapping of the hemiaminal with a cyanide source, allows for the straightforward synthesis of α‐amino nitriles. The methodology presented here, displays high levels of chemoselectivity allowing for the reduction of amides in the presence of functional groups such as ketones, imines, aldehydes, and acids, which affords a simple route for the synthesis of α‐amino nitriles with a broad scope of functionalities in high yields. Furthermore, the applicability of this methodology is demonstrated by scale up experiments and by derivatization of the target compounds into synthetically interesting products. The selective cyanation is successfully applied in late stage functionalizations of amide containing drugs and prolinol derivatives.     

Geometry of Discrete-Time Spin Systems

Classical Hamiltonian spin systems are continuous dynamical systems on the symplectic phase space \((S^2)^n\). In this paper, we investigate the underlying geometry of a time discretization scheme for classical Hamiltonian spin systems called the spherical midpoint method. As it turns out, this method displays a range of interesting geometrical features that yield insights and sets out general strategies for geometric time discretizations of Hamiltonian systems on non-canonical symplectic manifolds. In particular, our study provides two new, completely geometric proofs that the discrete-time spin systems obtained by the spherical midpoint method preserve symplecticity. The study follows two paths. First, we introduce an extended version of the Hopf fibration to show that the spherical midpoint method can be seen as originating from the classical midpoint method on \(T^*\mathbf {R}^{2n}\) for a collective Hamiltonian. Symplecticity is then a direct, geometric consequence. Second, we propose a new discretization scheme on Riemannian manifolds called the Riemannian midpoint method. We determine its properties with respect to isometries and Riemannian submersions, and, as a special case, we show that the spherical midpoint method is of this type for a non-Euclidean metric. In combination with Kähler geometry, this provides another geometric proof of symplecticity.     

The importance of alkali cations in the [{RuCl2(p-cymene)}2]-pseudo-dipeptide-catalyzed enantioselective transfer hydrogenation of ketones

We studied the role of alkali cations in the [{RuCl2(p-cymene)}2]-pseudo-dipeptide-catalyzed enantioselective transfer hydrogenation of ketones with isopropanol. Lithium salts were shown to increase the enantioselectivity of the reaction when iPrONa or iPrOK was used as the base. Similar transfer-hydrogenation systems that employ chiral amino alcohol or monotosylated diamine ligands are not affected by the addition of lithium salts. These observations have led us to propose that an alternative reaction mechanism operates in pseudo-dipeptide-based systems, in which the alkali cation is an important player in the ligand-assisted hydrogen-transfer step. DFT calculations of the proposed transition-state (TS) models involving different cations (Li+, Na+, and K+) confirm a considerable loosening of the TS with larger cations. This loosening may be responsible for the fewer interactions between the substrate and the catalytic complex, leading to lower enantiodifferentiation. This mechanistic hypothesis has found additional experimental support; the low ee obtained with [BnNMe3]OH (a large cation) as base can be dramatically improved by introducing lithium cations into the system. Also, the complexation of Na+, K+, and Li+ cations by the addition of [15]crown-5 and [18]crown-6 ethers and cryptand 2.1.1 (which selectively bind to these cations and, thus, increase their bulkiness), respectively, to the reaction mixture led to a significant drop in the enantioselectivity of the reaction. The lithium effect has proved useful for enhancing the reduction of different aromatic and heteroaromatic ketones.     

Ion diode logics for pH control

Electronic control over the generation, transport, and delivery of ions is useful in order to regulate reactions, functions, and processes in various chemical and biological systems. Different kinds of ion diodes and transistors that exhibit non-linear current versus voltage characteristics have been explored to generate chemical gradients and signals. Bipolar membranes (BMs) exhibit both ion current rectification and water splitting and are thus suitable as ion diodes for the regulation of pH. To date, fast switching ion diodes have been difficult to realize due to accumulation of ions inside the device structure at forward bias--charges that take a long time to deplete at reverse bias. Water splitting occurs at elevated reverse voltage bias and is a feature that renders high ion current rectification impossible. This makes integration of ion diodes in circuits difficult. Here, we report three different designs of micro-fabricated ion bipolar membrane diodes (IBMDs). The first two designs consist of single BM configurations, and are capable of either splitting water or providing high current rectification. In the third design, water-splitting BMs and a highly-rectifying BM are connected in series, thus suppressing accumulation of ions. The resulting IBMD shows less hysteresis, faster off-switching, and also a high ion current rectification ratio as compared to the single BM devices. Further, the IBMD was integrated in a diode-based AND gate, which is capable of controlling delivery of hydroxide ions into a receiving reservoir.     

Alkali sulfation during combustion of coal in a pilot scale facility using additives to alter the global sulfur to potassium and chlorine to potassium ratios

Due to the urgent needs to reduce anthropogenic carbon dioxide emissions there is an increasing interest in the use of alternative fuels. For this reason, there is a need for new knowledge on how to design and adapt existing heat and power plants to biogenic and waste-derived fuels. This work relates to co-firing of biomass and coal and the sulfation of alkali chlorides in coal-fired flames doped with chemical additives. We aim to examine the global time scales of alkali sulfation and chlorination based on combustion experiments that were conducted in a 30-kW coal flame. Temperature, gas and particle composition measurements were conducted. Both experiments and modelling support that the apparent alkali sulfation kinetics are fast in a coal-fired flame and that it is dominated entirely by the presence of SO₂. The availability of oxygen and carbon monoxide, or hydrocarbons, is also critical to sustain the sulfation reaction cycle; low concentrations are sufficient. For industrial boilers this implies that sulfur addition, in combination with reburning, should constitute an efficient strategy to mitigate alkali-chlorination and the related high temperature corrosion.