Polypyrrole films electropolymerized from ionic liquids and in a traditional liquid electrolyte: A comparison of morphology and electro-optical properties

Polypyrrole (pPy) films have been formed by electropolymerization from a conventional media: lithium triflate in acetonitrile and in room temperature ionic liquids: 1-ethyl-3-methyl imidazolium bis(perfluoroethanesulfonyl)imide (EMIPFSI) and 1-ethyl-3-methylimidazolium trifluoromethanesulfonate (EMITF). The well ordered nodular morphology of the pPy film grown in EMIPFSI with significantly low roughness endows these films with superior redox activity and electro-optical properties. Ambient temperature dc conductivities of 43, 15 and 13 S cm⁻¹, for films grown in EMIPFSI, EMITF and control solutions have seen obtained. The well-organized particulate morphology of the pPy film grown in EMIPFSI seems to be responsible for its enhanced conductivity, as also better interfacial charge transfer capabilities as compared to their counterparts derived. Under an external bias of ±2.2 V, the sluggish switching kinetics shown by the films under scrutiny presumably are due to the (i) resistive barriers formed at the two interfaces of the pPy electrode (ii) a plausible passivation layer on the solution side of the film during electrochemical cycling. This demonstrates the need to further improve the interfacial properties of pPy so as to obtain a consistent and stable electrochromic response.     

Enantio- and diastereoselectivities in chiral sulfur ylide promoted asymmetric aziridination reactions

Density functional theory investigation on the factors controlling enantio- and diastereoselection in asymmetric aziridination reaction by the addition of chiral bicyclic sulfur ylides to substituted aldimines is presented. High levels of enantioselection are predicted toward the formation of (2S,3S)-cis and (2R,3S)-trans aziridines by the addition of stabilized ylide (R = COMe) respectively to SO2Me and CO2Me protected aldimines. Similarly, high %ee is predicted for the formation of (2S,3R)-cis aziridines from semistabilized (R = Ph) ylide. Moderate to high levels of diastereoselectivity is noticed as well. The present study highlights that a correct prediction on extent of enantioselection requires the knowledge of the activation barriers for elementary steps beyond the initial addition step. In the case of stabilized ylides the ring-closure (or elimination of sulfur compound) is found to be crucial in controlling enantio- and diastereoselection. A cumulative effect of electronic as well as other weak interactions is identified as factors contributing to the relative energies of transition states leading to enantio- and diastereomeric products for the stabilized ylide addition to aldimines. On the contrary, steric control appears quite dominant with semistabilized ylide addition. With the smallest substituent on ylide (R = Me), high enantioselectivity is predicted for the formation of (2R,3R)-trans aziridines although the %de in this case is found to be very low.     

5-Carboxy-2-azabicyclo[2.1.1]hexanes as precursors of 5-halo, amino, phenyl, and 2-methoxycarbonylethyl methanopyrrolidines

Novel 5-X-substituted-2-azabicyclo[2.1.1]hexanes (X = 5-syn-Cl, -Br, -I, -Ph, -NHCOOR (R = Me, Bn, t-Bu), -CH2CH2COOMe and X = 5-anti-Br, -I, -Ph) were synthesized from the X = 5-syn-carboxy derivative. New 5-anti-X-2-azabicyclo[2.1.1]hexanes, X = NHCOOR (R = Me, Bn), were prepared stereoselectively from the X = 5-anti-carboxy substrate.     

Branch-and-bound algorithms for scheduling in permutation flowshops to minimize the sum of weighted flowtime/sum of weighted tardiness/sum of weighted flowtime and weighted tardiness/sum of weighted flowtime,weighted tardiness and weighted earliness of jobs

The problem of scheduling in permutation flowshops is considered in this paper with the objectives of minimizing the sum of weighted flowtime/sum of weighted tardiness/sum of weighted flowtime and weighted tardiness/sum of weighted flowtime, weighted tardiness and weighted earliness of jobs, with each objective considered separately. Lower bounds on the given objective (corresponding to a node generated in the scheduling tree) are developed by solving an assignment problem. Branch-and-bound algorithms are developed to obtain the best permutation sequence in each case. Our algorithm incorporates a job-based lower bound (integrated with machine-based bounds) with respect to the weighted flowtime/weighted tardiness/weighted flowtime and weighted tardiness, and a machine-based lower bound with respect to the weighted earliness of jobs. The proposed algorithms are evaluated by solving many randomly generated problems of different problem sizes. The results of an extensive computational investigation for various problem sizes are presented. In addition, one of the proposed branch-and-bound algorithms is compared with a related existing branch-and-bound algorithm.     

Conversion electron measurements and determination of rotational parameters in 177Lu and 177Hf

We discuss the possibility whether superheavy elements can be produced in Nature by the astrophysical rapid neutron capture process. To this end we have performed fully dynamical network r-process calculations assuming an environment with neutron-to-seed ratio large enough to produce superheavy nuclei. Our calculations include two sets of nuclear masses and fission barriers and include all possible fission channels and the associated fission yield distributions. Our calculations produce superheavy nuclei with $\ensuremath A\approx 300$ that however decay on time scales of days.     

Effect of cationic precursor pH on optical and transport properties of SILAR deposited nano crystalline PbS thin films

The lead sulfide (PbS) thin films were deposited on glass substrate using successive ionic layer adsorption and reaction (SILAR) method at different pH of the cationic precursor, keeping the pH of the anionic precursor invariant. In this work, we establish that the pH of the cationic precursor and in turn the size of the crystallites affects the optical and electrical properties of PbS thin films. The characterization of the film was carried out using X-ray diffraction, scanning electron microscopy, optical and electrical measurement techniques. The presence of nanocrystallites was revealed by optical absorption and structural measurements. The PbS thin films obtained under optimal deposition conditions were found to be polycrystalline with face centered cubic structure. The lattice parameter, grain size, micro strain, average internal stress and dislocation density in the film were calculated and correlated with pH of the solution. The values of average crystallite size were found to be in the range 16-23 nm. Optical studies revealed the existence of direct and indirect band gap values in the range 0.99-1.84 eV and 0.60-0.92 eV, respectively. The room temperature resistivity of the synthesized PbS films was in the range of 1.2 × 10⁷ to 3.5 × 10⁷ Ω cm.