Dithioannulation of Alkynes

A direct method for the preparation of 2,3-diphenyl-1,4-dithiins has been developed. The process involves treating alkynes with nickel bisdiphenyl-dithiolene in refluxing chlorobenzene in the presence of pyridine. Pyridine appears to be essential in order to avoid further transformation of 1,4-dithiins to thiophenes.     

Theoretical study of the electronic nonadiabatic transitions in the photoelectron spectroscopy of F2O

The photoelectron spectrum of F2O pertaining to ionizations to the ground (X2B1) and low-lying excited electronic states (A2B2, B2A1, and C2A2) of F2O+ is investigated theoretically. The near equilibrium potential energy surfaces of the ground electronic state (X2B1) of F2O and the mentioned ground and excited electronic states of F2O+ reported by Wang et al. ( J. Chem. Phys. 2001, 114, 10682) for the C2v configuration are extended for the Cs geometry assuming a harmonic vibration along the asymmetric stretching mode. The vibronic interactions between the A2B2 and B2A1 electronic states of F2O+ are treated within a linear coupling approach, and the strength of the vibronic coupling parameter is calculated by an ab initio method. The nuclear dynamics is simulated by both time-independent quantum mechanical and time-dependent wave packet approaches. Although the first photoelectron band exhibits resolved vibrational progression along the symmetric stretching mode, the second one is highly overlapping. The latter is attributed to the nonadiabatic interactions among the energetically close A2B2, B2A1, and C2A2 electronic states of F2O+. The theoretical findings are in good accord with the available experimental results.     

A convergent total synthesis of a new antiepileptic ceramide and its triacetyl derivative using olefin cross metathesis

A convergent total synthesis of a new antiepileptic ceramide 1b and its triacetyl derivative 1b′ was completed by using two important C-C bond forming reactions, Wittig methylenation and olefin cross metathesis as the key steps. The easily available 3,4,6-tri-O-benzyl-d-galactal was used as a chiral pool for the synthesis of highly functionalized amide 3 and the commercially available 1,12-dodecanediol for the long chain olefin counterpart 4. The long hydrocarbon chain of the new ceramide 1b was installed by using olefin cross metathesis between amide 3 and long chain terminal olefin 4 followed by hydrogenation.     

The effect of the finite size of ions and Debye layer overspill on the screened Coulomb interactions between charged flat plates

Screened repulsion between uniformly charged plates with an intervening electrolyte is analyzed for strongly overlapped electrical double layers (EDL), accounting for the steric effect of ions and their expulsion from EDL edges into the surrounding solution. As a generalization of a study by Philipse et al. which does not account for these effects, an analytical expression is derived for the repulsion pressure in the limit of infinitely long plates with a zero-field assumption, which agrees closely with the corresponding numerical solution at low inter-plate separations. Our results show an augmented repulsive pressure for finite-sized ions at strong EDL overlaps. For plates with a finite lateral size, we demonstrate a further extended domain of low inter-plate gaps where the repulsion pressure increases with ion size due to a strong interplay between the steric interaction of ions and the EDL overspill phenomenon, considered earlier in a study by Ghosal & Sherwood limited to the linear Debye-Hückel regime (which cannot account for the steric effect of ions). This investigation on a simple model should enhance our understanding of the interaction between charged particles in electrophoresis, nanoscale self-assembly, active particles, and various other electrokinetic systems.     

Surfactant-colligend particle size effects on ion flotation: Influences of mixing time,temperature, and surfactant chain length

Summary The ion flotation of Cr(VI) from 0.926 x 10^–3 M aqueous suspensions at pH 4.1 is related to particle size distribution data, obtained by filtration of the surfactant-Cr(VI) suspensions prior to flotation. The effects of surfactant-Cr(VI) mixing (precipitation and aggregation) time and of temperature are established over 10–45 °C, with particle size and flotation generally increasing with temperature. Five, rather high purity, quaternary ammonium surfactants are used, with chain lengths from C₁₀ to C₁₈. The optimum chain length at 13° and 23 °C is C14 and at 33° and 43 °C is C16. An increase in the molar surfactant/Cr(VI) ratio in the initial suspension improves flotation until values of the ratio of 1.1, 1.2, and 2.2 are exceeded for C₁₆, C₁₈, and C₁₄ surfactants, respectively. The four roles of a surfactant in ion flotation — as a precipitant, as a dispersant (with surface adsorption opposing aggregation), as a collector, and as a frother — are discussed in terms of flotation, particle size distributions, and surface charge measurements.

---

Zusammenfassung Die Flotation von Cr(VI)-Ionen aus 0.926 × 10^–3 M wässeriger Suspension bei pH 4.1 steht in Beziehung zu der Verteilung der Teilchengröße, die sich durch Filtration einer Suspension von Benetzungsmittel-Cr (VI) vor der Flotation ergibt. Die Wirkung von Benetzungszeit (=Fällung und Zusammenballen) sowie der Temperatur im Bereich von 10–45 °C wurden untersucht; Teilchengröße und Flotation nehmen im allgemeinen mit steigender Temperatur zu. Fünf quaternäre Ammonium-Benetzungsmittel hoher Reinheit und mit Kettenlängen von C₁₀ bis C₁₈ wurden benutzt. Die optimale Kettenlänge bei 13° und 23 °C ist C₁₄, bei 33° und 43 °C dagegen C₁₆. Eine Vergrößerung des Verhältnisses von Benetzungsmittel:Cr(VI) in der anfänglichen Suspension ist für die Flotation so lange vorteilhaft, bis die Verhältniswerte 1.1 (C₁₆), 1.2 (C₁₈) bzw. 2.2 (C₁₄) überschritten werden. Die vier Aufgaben des Benetzungsmittels in einer Ionenflotation — als Fällungsmittel, Verteilungsmittel (die Oberflächenadsorption wirkt der Zusammenballung entgegen), Sammler und Schaummittel — werden in Bezug auf die Flotation, die Verteilung der Teilchengröße und Messungen der Oberflächenladung diskutiert.

     

Magnetoelectronic transport of the two-dimensional electron gas in CdSe single quantum wells

Hall mobility and magnetoresistance coefficient for the two-dimensional (2D) electron transport parallel to the heterojunction interfaces in a single quantum well of CdSe are calculated with a numerical iterative technique in the framework of Fermi-Dirac statistics. Lattice scatterings due to polar-mode longitudinal optic (LO) phonons, and acoustic phonons via deformation potential and piezoelectric couplings, are considered together with background and remote ionized impurity interactions. The parallel mode of piezoelectric scattering is found to contribute more than the perpendicular mode. We observe that the Hall mobility decreases with increasing temperature but increases with increasing channel width. The magnetoresistance coefficient is found to decrease with increasing temperature and increase with increasing magnetic field in the classical region.      

Stereoselective total synthesis of Jaspine B (Pachastrissamine) utilizing iodocyclization and an investigation of its cytotoxic activity

The stereoselective synthesis of Jaspine B has been achieved from easily available (S)-Garner’s aldehyde. The trisubstituted tetrahydrofuran core of Jaspine B was constructed by utilizing a diastereoselective iodocyclization as the key step. Deiodination and debenzylation were performed in a single step by using n-Bu₃SnH and ABCN as a conjugate catalyst system. The in vitro cytotoxicity of compounds 1 and 1a against 3 human cancer cell lines-A549 (lung), MCF7 (breast), and KB (oral); and a non-cancer cell line (NIH3T3) was determined by sulphorhodamine B based assay.     

Almost strict competitiveness in extensive games

We consider an extension of an almost strictly competitive game, introduced by Aumann (1961), inn-person extensive games by incorporating Selten's subgame perfection. We call it a subgame perfect weakly-almost (SPWA) strictly competitive game, in particular, an SPWA strictly competitive game in strategic form is simply called a WA strictly competitive game. We give some general results on the structure of this class of games. One result gives an easy way to verify almost strict competitiveness of a given extensive game. We show that a two-person weakly unilaterally competitive extensive game, introduced by Kats and Thisse (1992) for normal form games, is SPWA strictly competitive. We remark that some of our main results for SPWA strictly competitive games do not hold for the modification of almost strict competitiveness with trembling-hand perfection.The author is indebted to Mamoru Kaneko for valuable discussions, comments and criticism throughout the paper. He thanks N. Bose, M. Frascatore, R. Gilles, H. Haller, A. Kats, J. Kline and an anonymous referee for helpful comments on earlier drafts. The usual disclaimer applies.     

Role of confinements on the melting of Wigner molecules in quantum dots

We explore the stability of a Wigner molecule (WM) formed in confinements with differentgeometries emulating the role of disorder and analyze the melting (or crossover) of such asystem. Building on a recent calculation [D. Bhattacharya, A. Ghosal, Eur. Phys. J.B 86, 499 (2013)] that discussed the effects of irregularities on thethermal crossover in classical systems, we expand our studies in the untested territory byincluding both the effects of quantum fluctuations and ofdisorder. Our results, using classical and quantum (path integral)Monte Carlo techniques, unfold complementary mechanisms that drive the quantum and thermalcrossovers in a WM and show that the symmetry of the confinement plays no significant rolein determining the quantum crossover scale n_X. This is because thezero-point motion screens the boundary effects within short distances. The phase diagramas a function of thermal and quantum fluctuations determined from independent criteria isunique, and shows “melting” from the WM to both the classical and quantum “liquids”. Anintriguing signature of weakening liquidity with increasing temperature, T, is found in the extreme quantum regime. The crossover is associated with production of defects. However, thesedefects appear to play distinct roles in driving the quantum and thermal “melting”. Ouranalyses carry serious implications for a variety of experiments on many-particle systems? semiconductor heterostructure quantum dots, trapped ions, nanoclusters, colloids and complex plasma.