Low band-gap benzodithiophene-thienothiophenecopolymers: the effect of dual two-dimensional substitutions on optoelectronic properties

Two new conjugated copolymers,PBDT-T6-TTF and PBDT-T12-TTF,were derived from a novel 4-fluorobenzoyl thienothiophene(TTF).In addition,two types of benzodithiophene(BDT)units with 2,3-dihexylthienyl(T6)and 2,3-didodecylthienyl(T12)substituents,respectively,were successfully synthesized.The effect of the dual two-dimensional(2D)substitutions of the building blocks upon the optoelectronic properties of the polymers was investigated.Generally,the two polymers exhibited good solubility and broad absorption,showing similar optical band gaps of~1.53 e V.However,PBDT-T6-TTF with its shorter alkyl chain length possessed a larger extinction coefficient in thin solid film.The highest occupied molecular orbital(HOMO)level of PBDT-T6-TTF was located at–5.38 e V while that of PBDT-T12-TTF was at–5.51 e V.In space charge-limitedcurrent(SCLC)measurement,PBDT-T6-TTF and PBDT-T12-TTF displayed respective hole mobilities of 3.0×10–4 and1.6×10–5 cm2 V1 s1.In polymer solar cells,PBDT-T6-TTF and PBDT-T12-TTF showed respective power conversion efficiencies(PCEs)of 2.86%and 1.67%.When 1,8-diiodooctane(DIO)was used as the solvent additive,the PCE of PBDT-T6-TTF was remarkably elevated to 4.85%,but the use of DIO for the PBDT-T12-TTF-blend film resulted in a lower PCE of 0.91%.Atomic force microscopy(AFM)indicated that the superior efficiency of PBDT-T6-TTF with 3%DIO(v/v)should be related to the better continuous phase separation of the blend film.Nevertheless,the morphology of the PBDT-T12-TTF deteriorated when the 3%DIO(v/v)was added.Our results suggest that the alkyl-chain length on the 2D BDT units play an important role in determining the optoelectronic properties of dual 2D BDT-TT-based polymers.     

Oscillations of reactivity in the [2+4]-cycloaddition of methyl acrylate to furan

The kinetics of [2+4]-cycloaddition of methyl acrylate to furan (Diets—Alder reaction) were studied at 70°C and 907 MPa,i.e., under conditions where the solvent (benzene) exists in the solid state. It was found that the reactivity exhibits oscillations with astronomic time and that its averaging leads to reaction rate constants, which are close to those expected from the calculations, carried out using the known reaction and activation volume effects and the reactivity at a pressure close to the atmospheric pressure.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2450–2455, October, 1996.     

Semiempirical quantum chemical calculations of molecular π- complexes

A method is suggested to calculate the geometrical and thermodynamical characteristics of organic π- complexes. The interaction energy is considered as a sum of two terms: the specific quantum chemical interaction of the π- electron systems depending essentially on the chemical nature of reactants, and the nonspecific atom-atom (van-der-Waals) interaction depending only on the kind of atoms belonging to the fragments of a complex. An attractive quantum chemical interaction is described in terms of the PPP-method; the van-der-Waals interaction is expressed in terms of the empirical exp-6-potential. The geometries of complexes are found by the complete energy minimization with respect to six parameters characterizing the mutual orientation of the complex fragments. Energies, entropies and equilibrium constants of several tetracyanoethylene π-complexes are calculated by this method. The results agree satisfactorily with experimental data.     

2-Phenylsulfinylmethyl-1,3-butadiene in the thermal Diels-Alder reaction

Russian Chemical Bulletin -     

Selection of surfactants for cell lysis in chemical cytometry to study protein-DNA interactions

Protein-DNA interactions play a defining role in many cellular processes. Studying such interactions at the single-cell level is important and challenging. Here we make the first step toward achieving this goal with chemical cytometry. Chemical cytometry utilizes capillary separation for detailed chemical analyses of single cells. The cell is injected into a capillary, lysed, and its components are analyzed by CE or capillary chromatography with highly sensitive detection. In order to apply chemical cytometry to studies of protein-DNA interactions, cell lysis must not destroy protein-DNA complexes. Surfactants represent the most practical means of cell lysis inside the capillary. This work aimed at finding surfactants and lysis conditions that do not destroy protein-DNA complexes. We studied three groups of surfactants--ionic, zwitterionic, and nonionic--with respect to their ability to lyse the cell membrane without significantly influencing the stability of protein-DNA complexes. Nonequilibrium CE of equilibrium mixtures with surfactants in the equilibrium mixtures and in the run buffer was used to measure the equilibrium constant, K(d), and rate constant, k(off), of protein-DNA complex dissociation. We found that nonionic surfactants worked best: they lyse the plasma membrane without significantly influencing K(d), k(off), or the EOF. This work creates the foundation for studies of protein-DNA interactions in single cells by chemical cytometry.