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Kerogens from the anoxic sediments of the Cariaco Basin spanning the last 130 ky were analyzed in order to determine the organic matter (OM) preservation pathways, and the evolution of these pathways with time. The kerogens were isolated using a protocol avoiding the formation of artificial melanoidins. Bulk elemental content, spectroscopic and pyrolytic features of the kerogens show that sulfurization is an important process in the insolubilisation of the OM, even in the most recent sample studied (~ 400 a). The degree of OM sulfurization on the studied interval depends on the redox conditions of the sediment during deposition and is largely correlated to the total organic carbon content of the sediment. A trend of downward increasing sulfurization of the organic matter is observed in the sediments of the studied two interglacials. From the available porewater analyses of Cariaco sediments and comparison with Black Sea sediments, the data suggest that downward progressive sulfurization of the OM is mainly due to the production of H2S by sulfate-dependent anaerobic oxidation of methane occurring at the sulfate/methane transition zone located a few meters below sea floor.

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Bent-core mesogens with thiophene and 2,2?-bithiophene units at the periphery of the aromatic core were synthesized and investigated by polarizing microscopy, XRD and electrooptical methods. Resorcinol, 2,7-naphthalenediol and 3,4?-biphenyldiol were used as bent units, phenyl thiophene-2-carboxylates form the rod-like wings and n-alkyl chains as well as olefin- and silylated-terminated alkyl chains were attached as flexible end-groups. A broad variety of different mesophase structures, incorporating ferroelectric and antiferroelectric switching smectic as well as modulated smectic phases, was obtained. Compared with the corresponding benzoates, these thiophene derived compounds form nearly identical LC phase structures, but have significantly reduced transition temperatures, which make them advantageous for applications.

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Chemical or electrochemical oxidation of substituted dithieno [3,4- b:3′,4′-d]thiophenes provides polymers with defined regiochemical structures. These materials have lower bandgaps (0.7-0.9 eV) than the unsubstituted fused heteroarene. Potential cycling of the 1,3-dimethyl substituted polymer film shows repetitive p- and n-dopability. The chemically-prepared dioctyl analog is soluble in common solvents such as chloroform, dichloromethane and THF. However, overoxidation of the polymers at an electrode surface presents a limitation to the polymerization of substituted analogs of the parent fused heteroarene.

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Thiophene nucleus has shown various biological activities like antibacterial, analgesic, antitumor, anti-inflammatory and used as building blocks for synthesis of agrochemicals. It has applications as metal chelating agents and in the development of insecticides. Due to excellent chelation, studies on metal chelates with Schiff bases of thiophene nucleus have received good attention. In the present study, the complexes of Co (II), Ni (II), Cu (II) and Zn (II) with Schiff base 3-(2-(thiophen-2-yl methylene) hydrazinyl)-2H-benzo [b] [1,4] oxazin-2-one (TM-HBO) derived from Thiophene-2-carboxaldehyde and 3-Hydrazino-1,4-benzoxazine-2-one (HBO) have been synthesized. The ligand acts as bis-bidentate ONNN/ONNS donor. The characterization of the ligand was done by LC-MS, IR, 1H NMR and electronic spectral studies. Characterization of the complexes was done by elemental analysis, molar conductivity studies, magnetic susceptibility studies, thermal studies, IR, electronic, ESR spectral studies etc. The geometrical structures have been found to be octahedral and square planar/octahedral. Degradation pattern of the compounds is shown by thermal studies. Thermal stabilities of Co (II), Ni (II), Cu (II) and Zn (II) complexes of TM-HBO were calculated by TGA analysis. The Kinetic parameters-energy of activation (Ea), enthalpy (DeltaH), entropy (DeltaS) and free energy changes (DeltaG) have been determined by thermogravimetric data. Coats-Redfern integration method with thirteen kinetic models was used to calculate the kinetic and thermodynamic parameters for the degradation of all the complexes. The stability of the ligand and Cu (II) complex were obtained from their molecular orbital structures from which the quantum chemical parameters were calculated using the HOMO-LUMO energies.

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A mild protocol for the synthesis of diaryl and heteroaryl sulfides is described. In a one-pot procedure, thiols are converted to sulfenyl chlorides and reacted with arylzinc reagents. This method tolerates functional groups including aryl fluorides and chlorides, ketones, as well as N-heterocycles including pyrimidines, imidazoles, tetrazoles, and oxadiazoles. Two compounds synthesized by this method exhibited selective activity against the MCF-7 breast cancer cell line in the micromolar range.

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Two N-heteroacene small molecules, P2BT and P2B2 T, with 2,1,3-benzodiathiazole end-capped N-heteroacene unit as the central building block have been designed and synthesized for bulk-heterojunction solar cells. Single-junction devices based on P2B2 T:PC71BM have achieved an impressive power conversion efficiency of 7.16% without any special treatment, which is the record efficiency among the N-heteroacene-based photovoltaics.

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A series of low band gap polymers composed of benzotriazole and benzo[1,2-b:4,5-b?]dithiophene derivatives were synthesized using a Stille cross-coupling reaction for use in organic photovoltaic devices. Linear or branched alkyl groups were incorporated into the benzothiazole-based accepting monomer part, and alkoxy or alkylthiophene groups were introduced to benzo[1,2-b:4,5-b?]dithiophene-based donating monomer part. Changes in photo-physical properties of the polymers by the structural modification of the donor-acceptor type low band gap polymers were investigated. The synthesized polymers were soluble in common organic solvents, and the resulting polymer solutions could be used to form smooth and uniform thin films by spin-casting. The synthesized polymers were found to exhibit good thermal stability, losing less than 5% of their weight upon heating to approximately 300C. The intra-molecular charge transfer interaction between the electron donating and electron accepting blocks in the polymeric backbone induced a broad absorption from 300 to 650 nm. The optical band gap energies of the polymers were measured to be 2.03-1.90 eV depending on the polymer structure. Solution-processed field-effect transistors were fabricated and characterized using the polymers as p-type channel materials. Bulk hetero-junction photovoltaic devices were fabricated using the polymers with [6,6]-phenyl C71-butyric acid methyl ester (PC71BM) as the electron acceptor. One of the fabricated device showed the maximum power conversion efficiency of 3.20% under AM 1.5 G (100 mW/cm2) conditions.

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Polymers play a vital role in every field. 1-Amino anthra-9,10-quinone combined with the copolymer poly(2-octylthiophene-co-3,4- ethylenedioxythiophene) was used to study the oxygen reduction reaction. This investigation reports the electrochemical characterisation of the combination of anthraquinone compound with the copolymer. From the cyclic voltammograms, the stability of the copolymer poly(2-octylthiophene-co-3,4-ethylenedioxy thiophene) was studied. From the chronoamperometric and chronocoulometric data?s, the diffusion coefficient values of anthraquinone at the copolymer modified electrode, influence of pH on the electrochemical behaviour and the number of electrons involved in anthraquinone reduction were determined. 1-Amino anthra-9,10-quinone combined with the conducting copolymer poly(2-octylthiophene-co-3,4- ethylenedioxythiophene) showed excellent electrocatalytic ability for the reduction of oxygen. Scanning electron microscopy images were included to show the excellent modification of the modified electrodes.

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Electrochemical deposition has been used to prepare a thin film of neutral 4?,4-(3-alkyl)-thiophene-5?,5-hydogen-nickel and copper dithiolenes (Ni-C2, Cu-C2). The application of molecular electrodeposition provides a means to solution process molecular semiconductors of poor solubility, which results from the strong intermolecular interaction required for charge transport. Both Ni-C2 and Cu-C2 form continuous thin films that show intense NIR absorptions, extending to 1800 nm and 2000 nm respectively giving evidence for the strong intermolecular interactions in the solid state. Both films are highly conducting and temperature dependence of resistance gave an activation energy of 0.42 eV and 0.072 eV respectively, with the near-metallic behaviour of Cu-C2 attributed to the additional presence of an unpaired electron.

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