Sep 2021 News Archives for Chemistry Experiments of 308087-58-3

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The p-type organic semiconductor (OSC) material tetrathieno[2,3-a:3?,2?-c:2?,3?-f:3?,2?-h]naphthalene (2TTN) and its alkyl-substituted derivatives Cn-2TTNs (n = 6, 8, and 10) have been developed based on the results of theoretical calculation-inspired investigation. A hole mobility for amorphous Cn-2TTNs (10-2-10-3 cm2 V-1 s-1) was accurately predicted by using a novel statistical method in which the geometric mean of the mobilities for many individual small molecular flocks in an amorphous solid was obtained by using molecular mechanical molecular dynamics simulations and quantum chemical calculations. The simulation also suggests that upon increasing the length of alkyl chains in Cn-2TTNs the mobilities become smaller as a consequence of a decrease in transfer integral values. Cn-2TTNs are synthesized in a microflow reactor through photoreactions of the corresponding precursors. Cn-2TTNs are then utilized in the fabrication of organic field-effect transistors (OFETs). Although spin-coated thin films of Cn-2TTNs are crystalline, the hole mobilities (10-2-10-3 cm2 V-1 s-1) of trial OFETs decrease upon elongation of the alkyl chains. This finding parallels the results of theoretical simulation. The simulation method for amorphous solids developed in this effort should become a useful tool in studies aimed at designing new OSC materials.

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A simple procedure leading to disposable potentiometric sensors using as a supporting electrode – electrical lead and transducer – a layer of carbon nanostructured material, either graphene or multiwalled nanotubes, is proposed, and the effect of the material used on the properties of the sensor is discussed. The obtained layers were partially covered with a conventional poly(vinyl chloride) (PVC) based ion-selective membrane to result in simple, planar, and disposable potentiometric sensors. The analytical performance of the thus obtained electrodes was compared with that of classical macroscopic all-solid-state ion-selective electrodes (e.g. employing poly(octylthiophene) as a solid contact and a similar ion-selective membrane). It was superior (taking into account detection limits or selectivity towards Na+ ions) compared to that of other disposable sensors proposed recently. The observed excellent analytical performance was attributed to the applied method of preparation of carbon nanostructured materials, which does not require addition of a surfactant to obtain a stable suspension (ink) used to prepare the electrical lead and the transducer of the sensor. Although the proposed sensors are predominantly intended for disposable use, pronounced stability of potential readings was obtained in within-day experiments. Moreover, due to their high conductivity carbon-plastic electrodes can be also applied in polarized potentiometric measurements.

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A novel polythiophene derivative, poly[3-(5-octyl-thienylene-vinyl)- thiophene] (POTVT) with conjugated thienylene vinyl side-chain, was synthesized, and the POTVT film shows a very broad absorption band-width covering from 300 nm to 700 nm after thermal annealing at 130C for 10 min. The Royal Society of Chemistry 2006.

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End groups in small-molecule photovoltaic materials are important owing to their strong influence on molecular stability, solubility, energy levels, and aggregation behaviors. In this work, a series of donor-acceptor pentads (D2-A-D1-A-D2) were designed and synthesized, aiming to investigate the effect of the end groups on the materials properties and photovoltaic device performance. These molecules share identical central A-D1-A triads (with benzodithiophene as D1 and 6-carbonyl-thieno[3,4-b]thiophene as A), but with various D2 end groups composed of alkyl-substituted thiophene (T), thieno[3,2-b]thiophene (TT), and 2,2?-bithiophene (BT). The results indicate a relationship between conjugated segment/alkyl chain length of the end groups and the photovoltaic performance, which contributes to the evolving molecular design principles for high efficiency organic solar cells.

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The syntheses of a series of (aralkylamino)- and (alkylamino)benzoic acids, as well as the corresponding esters and sodium salts, are described. The compounds were evaluated in vivo in rats for serum sterol and triglyceride lowering activity and in vitro for activity in inhibiting the principle cholesterol-esterifying enzyme of the arterial wall, fatty acyl-CoA:cholesterol acyltransferase (ACAT). Based on a combination of these two activities, cataben sodium (150) was selected for development as a hypolipidemic and potential antiatherosclerotic agent.

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Cross-coupling of alkyl halides with alkyl Grignard reagents proceeds with extremely high TONs of up to 1230000 using a Cu/unsaturated hydrocarbon catalytic system. Alkyl fluorides, chlorides, bromides, and tosylates are all suitable electrophiles, and a TOF as high as 31200 h-1 was attained using an alkyl iodide. Side reactions of this catalytic system, i.e., reduction, dehydrohalogenation (elimination), and the homocoupling of alkyl halides, occur in the absence of additives. It appears that the reaction involves the beta-hydrogen elimination of alkylcopper intermediates, giving rise to olefins and Cu-H species, and that this process triggers both side reactions and the degradation of the Cu catalyst. The formed Cu-H promotes the reduction of alkyl halides to give alkanes and Cu-X or the generation of Cu(0), probably by disproportionation, which can oxidatively add to alkyl halides to yield olefins and, in some cases, homocoupling products. Unsaturated hydrocarbon additives such as 1,3-butadiene and phenylpropyne play important roles in achieving highly efficient cross-coupling by suppressing beta-hydrogen elimination, which inhibits both the degradation of the Cu catalyst and undesirable side reactions.

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3,4-Ethylenedioxythiophene and 3-octylthiophene were electropolymerized on glassy carbon electrodes (GCE) to compare with four different electrolytes [lithium perchlorate (LiClO4), sodium perchlorate, tetraethylammonium tetrafluoroborate, and tetrabutylammonium tetrafluoroborate] in a solvent of acetonitrile (CH3CN). Modified electrodes were characterized by cyclic voltammetry, attenuated total reflectance-Fourier transform IR spectroscopy, scanning electron microscopy, energy dispersive X-ray analysis, atomic force microscopy, and electrochemical impedance spectroscopy (EIS). Nyquist and Bode plots for magnitude, phase, admittance, and capacitance on both polymer-modified electrodes were comparatively investigated in detail. The highest low-frequency capacitance (C LF) and double-layer capacitance (C dl) were obtained in 0.1 M LiClO4/CH3CN for poly(3,4-ethylenedioxythiophene) and poly(octylthiophene)/GCE. EIS data were fitted to the equivalent circuit model of R(Q(R(C(R(C(RW))))))(CR), which is used to investigate circuit parameters.

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The synthesis of conjugated acceptors based on thiadiazoloquinoxaline (TQ) derivatives is described. Apart from reporting on the functionalization of the TQ core, the influence of the substituents was studied by UV-vis absorption and emission spectroscopy, cyclic voltammetry measurements, and DFT calculations. By changing the donor as well as the ?-spacer, a fine-tuning of the photo- and electrochemical properties was achieved. 2011 American Chemical Society.

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The species and distributions of secondary compounds generated from eight organic sulfur compounds by way of hydrous pyrolysis were investigated. The results indicate that the formation of the secondary compounds and their structures and distribution depend on their thermal stability and the types of initial model compounds, as well as hydrous pyrolysis temperatures, while a large number and higher abundance of the secondary compounds appear to be formed mainly between 200 and 270C. Assignment of these secondary compounds indicates that alkyl thiols and sulfides are the most reactive compounds, producing a large number and relatively high amount of secondary organic thiols, sulfides, disulfides, sulfoxides and sulfones; while the secondary compounds generated from the thiophenic compounds are mainly low abundant methylated isomers of their own. Disulfidization, sulfidization and oxidation are the most significant mechanism(s) associated with the transformation of the initial thiols and sulfides model compounds. Alkyl thiophenes are only found to be formed from the alkyl thiol and sulfides, while it is noticed that thiophene, benzothiophene and dibenzothiophene are not genetically connected as they are not precursors of each other. Methylated thiophenic compounds are quantitatively insignificant but commonly present in the pyrolysates of thiophenes, benzothiophenes and dibenzothiophenes.

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Three pi-conjugated alternating copolymers, based on dibenzosilole as an electron-rich unit and fluorinated or non-fluorinated quinoxaline as an electron-withdrawing unit, connected through thiazole or thiophene moieties, have been synthesized, fully characterized and applied as donors in polymer solar cells (PSCs). The three copolymers, namely PDBS-TQx, PDBS-TQxF and PDBS-TzQx, belong to the wide band-gap semiconductor materials family, and they show an absorption edge in the visible region close to 650 nm. In order to tune the position of the polymer energy levels, and in particular to decrease their HOMO energy level, we compare the use of a thiazole spacer sandwiching the electron-deficient moiety as an alternative way to the popular backbone fluorination. PSCs based on a blend of PDBS-TQx and [6,6]-phenyl-C71-butyric acid methylester (PC71BM) as an active layer have shown the best device performances with a maximum power conversion efficiency (PCE) of 5.14% for the active area of 0.28 cm2 (under standard illumination of AM 1.5G, 1000 W m-2). Interestingly this polymer outperforms P3HT:(PC61BM) solar cells used as a reference material in this work. In addition to the thorough characterization data, including among other spectroscopy techniques, XRD, OFET, AFM and nc-AFM, we discuss in detail the relationship between the chemical structures of the three polymers, their optoelectronic properties, the phase separation in blends with PC71BM and their photovoltaic performances.

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Piperidine – Wikipedia,
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