574 research outputs found

    Pattern forming instability induced by light in pure and dye-doped nematic liquid crystals

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    We study theoretically the instabilities induced by a linearly polarized ordinary light wave incident at a small oblique angle on a thin layer of homeotropically oriented nematic liquid crystal with special emphasis on the dye-doped case. The spatially periodic Hopf bifurcation that occurs as the secondary instability after the stationary Freedericksz transition is analyzed.Comment: 8 pages, 7 figures, LaTeX, accepted to Phys. Rev.

    ADDA and ADADA systems based on triphenylamine as molecular donors for organic photovoltaics

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    Three molecular donor (D) acceptor (A) systems of structure A–D–A–D–A as well as an A–D–D–A compound have been synthesized by spatial extension of reference D–A system containing a triphenylamine donor block (5). UV–Vis absorption spectroscopy, cyclic voltammetry and theoretical calculations show that the presence of a median acceptor group has limited effect on the internal charge transfer while direct dimerization leads to an increase of the effective conjugation length. A cursory evaluation of the new compounds as donor material in bilayer solar cells using fullerene C60 as the acceptor material shows that the presence of a median acceptor has deleterious effect on conversion efficiency while the simple dimerization of the molecule leads to a substantial improvement of the short-circuit current density and efficiency

    Poly(thiophenes) derivatized with linear and macrocyclic polyethers: from cation detection to molecular actuation

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    The association of linear or macrocyclic polyethers with the electronic properties of the π-conjugated polythiophene backbone leads to functional conducting polymers that exhibit metal cation dependent electronic properties. Based on this concept, various classes of cation sensors have been proposed and investigated for almost two decades. The interactions of metal cations with linear or macrocyclic polyether functional groups lead to modifications of the electronic properties of the π-conjugated backbone through various mechanisms including direct electronic effects on a single conjugated chain, collective electrochemical processes, or conformational changes. Conjugated polymers and oligomers representative of these various processes are discussed with an emphasis on recent examples of derivatized conjugated systems in which the interactions between metal cations and polyether groups serve as driving force to create molecular motion in conjugated systems

    Electronic structure of MgB2_2: X-ray emission and absorption studies

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    Measurements of x-ray emission and absorption spectra of the constituents of MgB2_2 are presented. The results obtained are in good agreement with calculated x-ray spectra, with dipole matrix elements taken into account. The comparison of x-ray emission spectra of graphite, AlB2_2, and MgB2_2 in the binding energy scale supports the idea of charge transfer from σ\sigma to π\pi bands, which creates holes at the top of the bonding σ\sigma bands and drives the high-Tc_cComment: final version as published in PR

    Optimization of a high work function solution processed vanadium oxide hole-extracting layer for small molecule and polymer organic photovoltaic cells

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    We report a method of fabricating a high work function, solution processable vanadium oxide (V2Ox(sol)) hole-extracting layer. The atmospheric processing conditions of film preparation have a critical influence on the electronic structure and stoichiometry of the V2Ox(sol), with a direct impact on organic photovoltaic (OPV) cell performance. Combined Kelvin probe (KP) and ultraviolet photoemission spectroscopy (UPS) measurements reveal a high work function, n-type character for the thin films, analogous to previously reported thermally evaporated transition metal oxides. Additional states within the band gap of V2Ox(sol) are observed in the UPS spectra and are demonstrated using X-ray photoelectron spectroscopy (XPS) to be due to the substoichiometric nature of V2Ox(sol). The optimized V2Ox(sol) layer performance is compared directly to bare indium–tin oxide (ITO), poly(ethyleneoxythiophene):poly(styrenesulfonate) (PEDOT:PSS), and thermally evaporated molybdenum oxide (MoOx) interfaces in both small molecule/fullerene and polymer/fullerene structures. OPV cells incorporating V2Ox(sol) are reported to achieve favorable initial cell performance and cell stability attributes

    Electron Transfer from Cyt b559 and Tyrosine-D to the S2 and S3 states of the water oxidizing complex in Photosystem II at Cryogenic Temperatures

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    The Mn4CaO5 cluster of photosystem II (PSII) catalyzes the oxidation of water to molecular oxygen through the light-driven redox S-cycle. The water oxidizing complex (WOC) forms a triad with Tyrosine(Z) and P-680, which mediates electrons from water towards the acceptor side of PSII. Under certain conditions two other redox-active components, Tyrosine(D) (Y-D) and Cytochrome b (559) (Cyt b (559)) can also interact with the S-states. In the present work we investigate the electron transfer from Cyt b (559) and Y-D to the S-2 and S-3 states at 195 K. First, Y-D (aEuro cent) and Cyt b (559) were chemically reduced. The S-2 and S-3 states were then achieved by application of one or two laser flashes, respectively, on samples stabilized in the S-1 state. EPR signals of the WOC (the S-2-state multiline signal, ML-S-2), Y-D (aEuro cent) and oxidized Cyt b (559) were simultaneously detected during a prolonged dark incubation at 195 K. During 163 days of incubation a large fraction of the S-2 population decayed to S-1 in the S-2 samples by following a single exponential decay. Differently, S-3 samples showed an initial increase in the ML-S-2 intensity (due to S-3 to S-2 conversion) and a subsequent slow decay due to S-2 to S-1 conversion. In both cases, only a minor oxidation of Y-D was observed. In contrast, the signal intensity of the oxidized Cyt b (559) showed a two-fold increase in both the S-2 and S-3 samples. The electron donation from Cyt b (559) was much more efficient to the S-2 state than to the S-3 state

    Macrocycles with bithiophene units: synthesis, structure, and electrochemical properties

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    Bithiophene macrocycles with oligo(oxyethylene) loops were synthesized in good yields by reacting 4,4-bis(hydroxymethyl)-2,2-bithiophene with ditosylated oligoethyleneglycols. The structures of the macrocycles were elucidated by NMR spectroscopy and MS spectrometry. The electronic and electrochemical properties of the macrocyclic compounds were determined using cyclic voltammetry and UV-Vis spectroscopy. (C) 2013 Elsevier Ltd. All rights reserved

    Integrated genomic analyses of ovarian carcinoma

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    A catalogue of molecular aberrations that cause ovarian cancer is critical for developing and deploying therapies that will improve patients’ lives. The Cancer Genome Atlas project has analysed messenger RNA expression, microRNA expression, promoter methylation and DNA copy number in 489 high-grade serous ovarian adenocarcinomas and the DNA sequences of exons from coding genes in 316 of these tumours. Here we report that high-grade serous ovarian cancer is characterized by TP53 mutations in almost all tumours (96%); low prevalence but statistically recurrent somatic mutations in nine further genes including NF1, BRCA1, BRCA2, RB1 and CDK12; 113 significant focal DNA copy number aberrations; and promoter methylation events involving 168 genes. Analyses delineated four ovarian cancer transcriptional subtypes, three microRNA subtypes, four promoter methylation subtypes and a transcriptional signature associated with survival duration, and shed new light on the impact that tumours with BRCA1/2 (BRCA1 or BRCA2) and CCNE1 aberrations have on survival. Pathway analyses suggested that homologous recombination is defective in about half of the tumours analysed, and that NOTCH and FOXM1 signalling are involved in serous ovarian cancer pathophysiology.National Institutes of Health (U.S.) (Grant U54HG003067)National Institutes of Health (U.S.) (Grant U54HG003273)National Institutes of Health (U.S.) (Grant U54HG003079)National Institutes of Health (U.S.) (Grant U24CA126543)National Institutes of Health (U.S.) (Grant U24CA126544)National Institutes of Health (U.S.) (Grant U24CA126546)National Institutes of Health (U.S.) (Grant U24CA126551)National Institutes of Health (U.S.) (Grant U24CA126554)National Institutes of Health (U.S.) (Grant U24CA126561)National Institutes of Health (U.S.) (Grant U24CA126563)National Institutes of Health (U.S.) (Grant U24CA143882)National Institutes of Health (U.S.) (Grant U24CA143731)National Institutes of Health (U.S.) (Grant U24CA143835)National Institutes of Health (U.S.) (Grant U24CA143845)National Institutes of Health (U.S.) (Grant U24CA143858)National Institutes of Health (U.S.) (Grant U24CA144025)National Institutes of Health (U.S.) (Grant U24CA143866)National Institutes of Health (U.S.) (Grant U24CA143867)National Institutes of Health (U.S.) (Grant U24CA143848)National Institutes of Health (U.S.) (Grant U24CA143843)National Institutes of Health (U.S.) (Grant R21CA135877
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