Monodisperse poly(triacetylene) oligomers extending from monomer to hexadecamer: joint experimental and theoretical investigation of physical properties

A series of monodisperse Et3-Si-end-capped poly(triacetylene) (PTA) oligomers ranging from monomer to hexadecamer was prepared by a fast and efficient statistical deprotection-oxidative Hay oligomerization protocol. The PTA oligomers exhibit an increasingly deep-yellow color with lengthening of the pi-conjugated backbone, feature excellent solubility in aprotic solvents, and exhibit melting points up to > 22 degrees C for the hexadecameric rod. This new dramatically extended oligo(enediyne) series now enables to investigate the evolution of the physico-chemical effects in PTAs beyond the linear 1/n versus property regime into the higher oligomer region where saturation becomes apparent. We report the results of joint experimental and theoretical studies, including analysis of the 13C NMR spectra, evaluation of the linear (UV/ Vis) and nonlinear [third-harmonic generation (THG) and degenerate four-wave mixing (DFWM)] optical properties, and characterization of the redox properties with cyclic and steady-state voltammetry. Up to the hexadecameric rod, an increasingly facile one-electron reduction step is observed, showing at the stage of the dodecamer, a leveling off tendency from the linear correlation between the inverse number of monomer units and the first reduction potential. The effective conjugation length (ECL) determined by means of UV/Vis spectroscopy revealed a pi-electron-delocalization length of about n = 10 monomeric units, which corroborates well with the oligomeric length for which in the 13C NMR spectrum C(sp2) and C(sp) resonances start to overlap. Third-harmonic generation (THG) and degenerate four-wave mixing (DFWM) measurements revealed for the second-order hyperpolarizability gamma a power law increase gammma-alpha-n(a) for oligomers up to the octamer with exponential factors a= 2.46+/-0.10 and a=2.64+/-0.20, respectively, followed by a smooth saturation around n = 10 repeating units. The power law coefficient a calculated with the help of the valence effective Hamiltonian (VEH) method combined to a sum-over-states (SOS) formalism corroborates well with the values found by both THG and DFWM experiments. Up to the PTA heptamer, INDO (intermediate neglect of differential overlap)-calculated gas-phase ionization potentials and electron affinities obey a linear relationship as a function of the inverse number of monomer units displaying a strong electron-hole symmetry. The onset of saturation for the electron affinity is calculated to occur around the octamer, in accordance with experimentally obtained results from electrochemical measurements.

[Transmembrane potential and ATP-ase activity of the plasma membrane of bacteria exposed to heavy metals]. / Transmembrannyi potentsial i ATP-aznaia aktivnost' plazmaticheskoi membrany bakterii pri vozdeistvii tiazhelykh metallov.

Effect of heavy metals (gold, zinc and cadmium) on the ATPase activity and transmembrane potential (delta psi) as integral index of bacterial cells membrane processes intensity has been studied. It was shown that studied membrane systems of bacteria are very sensitive to the action of heavy metals and they can serve as indicators of resistance of bacterial cultures.

[Effect of thallium of ATP-ase activity and transmembrane potential in bacteria]. / Vliianie talliia na ATP-aznuiu aktivnost' i transmembrannyi potentsial bakterii.

Effect of thallium (TlNO3) on the ATPase activity and transmembrane potential (Dj) of bacteria with different levels of resistance to this metal has been studied. The hypothesis has been made that the resistance biochemical mechanism is based on the energy transformation systems in the cell.

[Inducible surface proteins from some strains of Pseudomonas species bacteria while adapting to cobalt]. / Indutsibel'nye poverkhnostnye belki nekotorykh shtammov bakterii roda Pseudomonas v usloviiakh adaptatsii k kobal'tu.

The possibility of increasing resistance of some Pseudomonas strains to cobalt at adaptation to monotonous increasing its concentration was studied. Strains Pseudomonas fluorescens B5242 and Pseudomonas fluorescens B894 are capable to increase its resistance in such conditions via inducible synthesis of protective surface proteins. The molecular masses of such proteins were 55.0; 45.0 and 33.0 kDa for P. fluorescens B5242 strain.

[Inhibitory effect of lead ions on cells of some strains of Pseudomonas species bacteria]. / Izuchenie ingibiruiushchego vliianiia ionov svintsa na kletki nekotorykh shtammov bakterii roda Pseudomonas.

The inhibition effect of ionic lead on membrane ATPase activity, transmembrane potential (delta psi) and permeability level of the Pb-sensitive P. fluorescens B894 and Pb-resistant P. fluorescens B4252 bacteria cells have been studied. It have been shown that decreasing ATPase activity and transmembrane potential values and the increasing of permeability by lead are higher for Pb-sensitive strain then for Pb-resistant. It is suggested that mechanism of the ionic lead toxic effect deals with plasma membrane biochemical parameters (ATPase activity, value of delta psi) alterations and interruption of it barrier function.

[Bacterial cell membrane ATPase in assessing heavy metal toxicity]. / ATFaza plazmaticheskikh membran bakterii v otsenke toksichnosti tiazhelykh metallov.

Sensitivity of membrane ATPase to heavy metals was studied in bacterial stains Bacillus cereus ATCC 14579, Bacillus cereus B4368, and Alcaligenes eutrophus CH34 was studied. The inhibition effects of metals on membrane ATPase ranged in the same order (Au > Cu > Zn > Co > Mn) as their effects on the growth of cultures. It is suggested that membrane ATPase is one of the targets for the action of heavy metal ions within the microbial cell and, therefore, its activity may serve as an indicator of their toxicity.

Scaling law for second-order hyperpolarizability in poly(triacetylene) molecular wires.

Poly(triacetylenes) are rodlike molecules with electrons delocalized over a one-dimensional path. We show that they exhibit a power-law dependence of the second-order hyperpolarizability gamma on the monomer unit n for short molecules and a smooth saturation toward a linear increase in longer molecules. The power law of gamma?n(a) with a approximately 2.5 from dengenerate four-wave mixing and third-harmonic generation measurements is in good agreement with quantum-chemical calculations. The critical conjugation length for saturation in the three cases is shown to be approximately 60 carbon-carbon bonds, which indicates the upper boundary for the electron delocalization in such a one-dimensional molecular wire.