Nucleophilic additions to alkylidene bis(sulfoxides): stereoelectronic effects in vinyl sulfoxides

Conjugate additions of nucleophiles (e.g. enolates, amines and malonate anions) to bis(p-tolylsulfinyl)alkenes, alkylidene-1,3-dithiane-1,3-dioxides and alkylidene-1,3-dithiolane-1,3-dioxides have recently been published. Reasons for different selectivities and reaction rates will be discussed by consideration of steric and electronic effects. The preferred mode of attack can be explained by stereoelectronic effects (hyperconjugation) in the primarily carbanion, which is stabilized by n-->S-O-sigma* interaction with an antiperiplanar S=O group. Calculation of the transition states [BP86/aug-TZVP] for the addition of acetone enolate to the dithiane-derived alkylidene bis(sulfoxide) revealed that 6.6-7.3 kJ mol(-1) more energy is needed for an attack leading to a less-stabilized carbanion. Two axial S=O groups in dithiolane-derived alkylidene bis(sulfoxides) lead to a higher reactivity towards nucleophiles.     

The Fermi surface of [Formula: see text

The heavy-fermion compound [Formula: see text] has been studied using the fully relativistic spin-polarized mean muffin-tin orbital method within the local density approximation. Two separate calculations, one where the f electron is treated as a valence electron and the other where it is treated as part of the core, have been performed and the Fermi surface is obtained. The angular-dependent de Haas - van Alphen (dHvA) frequencies are calculated in both cases and they are compared with the experimental dHvA frequencies. We also calculated the electron momentum densities and compared them with the electron - positron momentum densities measured from the two-dimensional angular correlation of electron - positron annihilation radiation. The spin polarization of the Fermi surface is analysed and we present a new interpretation of the experimental data of Harrison et al.     

Graphene-induced apoptosis in lung epithelial cells through EGFR

Expanding interest in nanotechnology applied to electronic and biomedical fields has led to fast-growing development of various nanomaterials. Graphene is a single-atom thick, two-dimensional sheet of hexagonally arranged carbon atoms with unique physical and chemical properties. Recently, graphene has been used in many studies on electronics, photonics, composite materials, energy generation and storage, sensors, and biomedicine. However, the current health risk assessment for graphene has been relatively limited and inconclusive. This study evaluated the toxicity effects of graphene on the airway epithelial cell line BEAS-2B, which represents the first barrier of the human body to interact with airborne graphene particles. Our result showed that graphene can induce the cellular Ca²⁺ by phospholipase C (PLC) associated pathway by activating epidermal growth factor receptor (EGFR). Subsequently, inositol 1,4,5-triphosphate (IP₃) receptors activate the release of Ca²⁺ from the endoplasmic reticulum (ER) Ca²⁺ stores. Those Ca²⁺ signals further trigger the calcium-regulated apoptosis in the cell. Furthermore, the stimulation can cause EGFR upregulation, which have been demonstrated to associate with diseases such as lung cancer, chronic obstructive pulmonary disease (COPD), and cardiovascular diseases. This study highlights the additional health risk considering that it can function as a contributing factor for other respiratory diseases.     

Parallel greedy algorithms for packing unequal circles into a strip or a rectangle

Given a finite set of circles of different sizes we study the strip packing problem (SPP) as well as the Knapsack Problem (KP). The SPP asks for a placement of all circles within a rectangular strip of fixed width so that the variable length of the strip is minimized. The KP requires packing of a subset of the circles in a given rectangle so that the wasted area is minimized. To solve these problems some greedy algorithms were developed which enhance the algorithms proposed by Huang et al. (J Oper Res Soc 56:539–548, 2005). Furthermore, the new greedy algorithms were parallelized using a master slave approach. The resulting parallel methods were tested using the instances introduced by Stoyan and Yaskov (Eur J Oper Res 156:590–600, 2004). Additionally, two sets of 128 instances each for the SPP and for the KP were generated and results for these new instances are also reported.