Growth of poly(3,4‐ethylenedioxythiophene) films prepared by base‐inhibited vapor phase polymerization

Transparent [90% transmittance at 550 nm at a sheet resistance (R_s) of 279 Ω sq^?1] poly(3,4‐ethylenedioxythiophene) (PEDOT) films with electrical conductivities up to 1354 S cm^?1 are prepared using base‐inhibited vapor phase polymerization at atmospheric pressure. The influence of reaction conditions, such as temperature and growth time, on the film formation is investigated. A simple and convenient two‐electrode method is used for the in situ measurement of resistance, enabling to investigate the growth mechanism of polymer films and the influence of different parameters (relative humidity and the amount of oxidant) on the film growth. Low humidity exerts a detrimental effect on film growth and conductivity. In situ R_s measurements suggest that a large structural change occurs upon washing the PEDOT‐oxidant film. © 2014 Wiley Periodicals, Inc. J Polym Sci Part B: Polym. Phys. 2014 , 52, 561–571     

Generation of Mixed Anhydrides via Oxidative Fragmentation of Tertiary Cyclopropanols with Phenyliodine(III) Dicarboxylates

Oxidative fragmentation of tertiary cyclopropanols with phenyliodine(III) dicarboxylates in aprotic solvents (dichloromethane, chloroform, toluene) produces mixed anhydrides. The fragmentation reaction is especially facile with phenyliodine(III) reagents bearing electron-withdrawing carboxylate ligands (trifluoroacetyl, 2,4,6-trichlorobenzoyl, 3-nitrobenzoyl), and affords 95−98% yields of the corresponding mixed anhydride products. The latter can be straightforwardly applied for the acylation of various nitrogen, oxygen and sulfur-centered nucleophiles (primary and secondary amines, hydroxylamines, primary alcohols, phenols, thiols). Intramolecular acylation yielding macrocyclic lactones can also be performed. The developed transformation has bolstered the synthetic utility of cyclopropanols as pluripotent intermediates in diversity-oriented synthesis of bioactive natural products and their synthetic congeners. For example, it was successfully applied for the last-stage modification of a cyclic peptide to produce a precursor of a known histone deacetylase inhibitor.     

Sonogashira cross-coupling of 3-bromo-1,2-diones: an access to 3-alkynyl-1,2-diones

A new general method for the synthesis of enols of cyclic 3-alkynyl-substituted 1,2-diketones is developed. Sonogashira cross-coupling of silyl enolates of cyclic 3-bromo-cyclopentane- and 3-bromo-cyclohexane-1,2-diones with variety of substituted acetylenes afforded enols of cyclic 3-alkynyl-1,2-diones with good yields (up to 93%) in a short reaction time. The starting 3-bromo-1,2-diones are easily obtainable by direct bromination of 1,2-diones with NBS.     

A Cosmological Model of Holographic Brane Gravity

A cosmological scenario with two branes (A and B) moving in a 5-dimensional bulk is considered. As in the case of ecpyrotic and born-again braneworld models it is possible that the branes collide. The energy-momentum tensor is taken to describe a perfect barotropic fluid on the A-brane and a phenomenological time-dependent cosmological constant on the B-brane. The A-brane is identified with our Universe and its cosmological evolution in the approximation of a homogeneous and isotropic brane is analysed. The dynamics of the radion (a scalar field on the brane) contains information about the proper distance between the branes. It is demonstrated that the deSitter type solutions are obtained for late time evolution of the braneworld and accelerative behaviour is anticipated at the present time.     

Cyclic amino acid salts as catalysts for the asymmetric Michael reaction

Different chiral cyclic amino acid alkali metal and ammonium salts were used as catalysts for the asymmetric Michael addition of aldehydes to nitrostyrene. The reaction yield and stereoselectivity depend slightly on the salt cation. The highest yield of the reaction (up to 100%) was obtained with (S)-morpholine-3-carboxylic acid salts, which gave moderate to good enantioselectivities (up to 72% ee) and diastereoselectivities (dr up to 89:11) whereas the highest selectivity was obtained with proline sodium salt (ee 88%).     

Oxidation of cyclopentane-1,2-dione: a study with O labeled reagents

The asymmetric oxidation of 3-alkyl-cyclopentane-1,2-diones with the Ti(OⁱPr)₄/tartaric ester/t-BuOOH complex, which gives, in a cascade process, highly enantiomerically enriched γ-lactone acids, was studied by ¹⁸O isotopic labeling in the substrate and in the oxidant. The path of the labeled atoms was followed by ¹³C NMR spectroscopy. It was found that the oxidative ring cleavage of 1,2-dione proceeds via a Baeyer-Villiger-type oxidation mechanism.     

A short enantioselective synthesis of homocitric acid-γ-lactone and 4-hydroxy-homocitric acid-γ-lactones

A simple method for the synthesis of enantiopure homocitric acid γ-lactone and its 4-hydroxy analogues starting from spiro-γ-dilactone, in up to 74% isolated yield is described.     

Electron-phonon and vibronic couplings in the FMO bacteriochlorophyll a antenna complex studied by difference fluorescence line narrowing

The electron-phonon and vibronic couplings governing the spectral properties have been studied in the Fenna-Matthews-Olson (FMO) bacteriochlorophyll a (BChl a)-protein complex at 4.5 K using a spectrally selective difference fluorescence line-narrowing technique. The complex is a part of the light-harvesting system of green photosynthetic bacteria. Its lowest-energy absorption band, peaking at 826 nm and responsible for the fluorescence, is believed to be due to Q_y transitions of largely isolated molecules. One of the main merits of the used method compared with the more common fluorescence line narrowing is that the zero-phonon lines (ZPL) resonant with the excitation laser can be accurately measured, allowing precise determination of the Huang-Rhys (HR) factors, the main characteristics of the linear electron-phonon and vibronic coupling strengths. Over 60 individual vibrational modes of intra- and intermolecular origin have been resolved in the energy range of 45-1600 cm⁻¹. The small HR factors for these modes, ranging between 0.001 and 0.018, add up to a value of S_vib=0.38±0.07. The effective HR factor for the phonons, S_ph, was found clearly wavelength-dependent, varying from ∼0.7 at short wavelengths to ∼0.3 at the long-wavelength tail of the absorption spectrum. Coupling between the BChl a molecules is likely responsible for this wavelength dependence.     

Theoretical prediction and assignment of vicinal 1H-1H coupling constants of diastereomeric 3-alkoxy-6,7-epoxy-2-oxabicyclo[3.3.0]octanes

Spin-spin coupling constants between nuclei in NMR spectroscopy reflect their spatial arrangement. A number of calculation methods, applying different levels of theory, have been developed to support the stereochemical assignment of novel compounds. Nevertheless, revisions of the assignment of structures in the literature are not rare. In the present work, the reliability of the calculation methods amenable for a theoretical prediction of spin-spin coupling constants of vicinal protons to support correct stereochemical assignment of substitution at five-membered rings of 3-alkoxy-6,7-epoxy-2-oxabicyclo[3.3.0]octanes was studied. Experimental (3)J(H,H) coupling constants were compared with the coupling constants calculated for all possible diastereomers. The fully quantum chemical approach provided theoretical (3)J(H,H) coupling constants with an absolute deviation of no more than 1.1 Hz for 91% of the experimentally studied coupled spins, whereas the methods without quantum chemical geometry optimization resulted in completely unreliable predictions. Consequently, for a reliable stereochemical assignment of small and medium size molecules, the protocol for calculating the coupling constants based on the results of the quantum chemical geometry optimization is recommended.