Amplified quenching of a conjugated polyelectrolyte by cyanine dyes

The conjugated polyelectrolyte PPESO3 features a poly(phenylene ethynylene) backbone substituted with anionic 3-sulfonatopropyloxy groups. PPESO3 is quenched very efficiently (KSV > 10(6) M(-1)) by cationic energy transfer quenchers in an amplified quenching process. In the present investigation, steady-state and picosecond time-resolved fluorescence spectroscopy are used to examine amplified quenching of PPESO3 by a series of cyanine dyes via singlet-singlet energy transfer. The goal of this work is to understand the mechanism of amplified quenching and to characterize important parameters that govern the amplification process. Steady-state fluorescence quenching of PPESO3 by three cationic oxacarbocyanine dyes in methanol solution shows that the quenching efficiency does not correlate with the Forster radius computed from spectral overlap of the PPESO3 fluorescence with the cyanines' absorption. The quenching efficiency is controlled by the stability of the polymer-dye association complex. When quenching studies are carried out in water where PPESO3 is aggregated, changes observed in the absorption and fluorescence spectra of 1,1',3,3,3',3'-hexamethylindotricarbocyanine iodide (HMIDC) indicate that the polymer templates the formation of a J-aggregate of the dye. The fluorescence dynamics in the PPESO3/HMIDC system were probed by time-resolved upconversion and the results show that PPESO3 to HMIDC energy transfer occurs on two distinctive time scales. At low HMIDC concentration, the dynamics are dominated by an energy transfer pathway with a time scale faster than 4 ps. With increasing HMIDC concentration, an energy pathway with a time scale of 0.1-1 ns is active. The prompt pathway (tau < 4 ps) is attributed to quenching of delocalized PPESO3 excitons created near the HMIDC association site, whereas the slow phase is attributed to intra- and interchain exciton diffusion to the HMIDC.     

Energy transfer in the nanostar: the role of coulombic coupling and dynamics

We present a theoretical investigation of energy transfer in the phenylene ethynelene dendrimer known as the nanostar. Data from extensive molecular dynamics simulations are used to model the dynamical effects caused by torsional motion of the phenyl groups. We compare rate constants for energy transfer between the two-ring chromophore and the three-ring chromophore obtained via the F?rster model, the ideal dipole approximation (IDA), and the transition density cube (TDC) method, which has as its limit an exact representation of the Coulombic coupling. We find that the rate constants obtained with the TDC are extremely sensitive to the phenyl group rotation, whereas the constants computed with the F?rster model and the IDA are not. The implications of these results for the interpretation of recent pump-probe experiments on the nanostar are discussed in detail. Finally, we predict the temperature dependence of the rate constant for energy transfer.     

Cartier divisors versus invertible sheaves

We consider the original version of the author's example of an algebraic scheme carrying an invertible sheaf arising from no Cartier divisor.     

Biotites from tuffs located in Mendoza,Argentina, seen by Mössbauer spectroscopy

Several natural biotite samples were studied by M.E., electron microprobe and XRD. The M.E. parameters allow to group them as oxybiotites, normal biotites, chloritized biotites and muscovitized biotites. Mechanisms of oxybiotite formation and processes undergone by the rocks are discussed.     

Two formulas for the BR multiplicity

We prove a projection formula, expressing a relative Buchsbaum–Rim multiplicity in terms of corresponding ones over a module-finite algebra of pure degree, generalizing an old formula for the ordinary (Samuel) multiplicity. Our proof is simple in spirit: after the multiplicities are expressed as sums of intersection numbers, the desired formula results from two projection formulas, one for cycles and another for Chern classes. Similarly, but without using any projection formula, we prove an expansion formula, generalizing the additivity formula for the ordinary multiplicity, a case of the associativity formula.     

Effects of electron-hole excitations in ion-surface collisions

We investigate effects related to electron-hole pair production and atomic level shift in atom scattering at surfaces by using a recently proposed exactly soluble model. We show that electron-hole pair production weakens Stückelberg oscillations and enhances loss of memory of the initial atomic charge state for narrow bands because of the diffusion of an electron or hole captured by the band. Wide band materials tend to display memory loss at lower velocities than do narrow band materials. Allowing the atomic energy level to shift above the Fermi energy tends to reduce memory loss.