Controlled release of singlet oxygen using diphenylanthracene functionalized polymer nanoparticles.

Functionalized polymer nanoparticles react and store molecular oxygen for several weeks in the form of endoperoxides. On-demand controlled release of singlet oxygen by the particles is achieved by thermolysis.

Photophysical study of bis(naphthalimide)-amine conjugates: toward molecular design of excimer emission switching.

The fluorescence properties of two bis(1,8-naphthalimides) with amino-containing spacers are investigated, giving special emphasis to the observation of excimer emission. It is found that a minor elongation of the spacer by two methylene units gives rise to a quantitative shut-down of the broad and red-shifted excimer emission. Furthermore, a switching of this emission is established through manipulation of a photoinduced electron transfer process, which involves the amino spacer. Protons as well as protic solvents lead to substantial excimer emission with lifetimes of 12 to 27 ns. The excimer quantum yield takes a maximum value of Φ(f) = 0.07 (acetonitrile with 1 equiv trifluoroacetic acid). The increased virtual Stokes shifts (ca. 150 nm) as compared to the fluorescence of monomeric 1,8-naphthalimides are an alternative approach to obtain colored, significant, and long-lived fluorescence from these chromophores. As an additional excited state pathway, the occurrence of homo-Förster resonance energy transfer (homo-FRET) is established by fluorescence polarization measurements and calculation of the corresponding critical Förster radius (R(0) ca. 13 Å). The average interchromophore distance between the naphthalimides is estimated as 7.5 Å and 9.5 Å for the dyad with the shorter and the longer spacer, respectively. These observations and the absence of a rise time component for excimer emission are in agreement with the formation of a "loose" ground state dimer, which upon excitation undergoes a fast geometrical adjustment to the excimer structure where the chromophores are at contact distance.

Photonic superdiffusive motion in resonance line radiation trapping Partial frequency redistribution effects.

The relation between the jump length probability distribution function and the spectral line profile in resonance atomic radiation trapping is considered for partial frequency redistribution (PFR) between absorbed and reemitted radiation. The single line opacity distribution function [M. N. Berberan-Santos et al., J. Chem. Phys. 125, 174308 (2006)] is generalized for PFR and used to discuss several possible redistribution mechanisms (pure Doppler broadening; combined natural and Doppler broadening; and combined Doppler, natural, and collisional broadening). It is shown that there are two coexisting scales with a different behavior: the small scale is controlled by the intricate PFR details while the large scale is essentially given by the atom rest frame redistribution asymptotic. The pure Doppler and combined natural, Doppler, and collisional broadening are characterized by both small- and large-scale superdiffusive Levy flight behaviors while the combined natural and Doppler case has an anomalous small-scale behavior but a diffusive large-scale asymptotic. The common practice of assuming complete redistribution in core radiation and frequency coherence in the wings of the spectral distribution is incompatible with the breakdown of superdiffusion in combined natural and Doppler broadening conditions.

Photonic superdiffusive motion in resonance radiation trapping.

In this work we consider the relation between the jump length probability density function and the line shape function in resonance radiation trapping in atomic vapors. The two-sided jump length probability density function suitable for a unidimensional formulation of radiative transfer is also derived. As a side result, a procedure to obtain the Maxwell distribution of velocities from the Maxwell-Boltzmann distribution of speeds was obtained. General relations that give the asymptotic jump length behavior and the Levy flight parameter mu for any line shape are obtained. The results are applied to generalized Doppler, generalized Lorentz, and Voigt line shape functions. It is concluded that the lighter the tail of the line shape function, the less heavy the tail of the jump length probability density function, although this tail is always heavy, with mu < or =1.

Intra- and intermolecular heavy-atom effects on the fluorescence properties of brominated C60 polyads.

A series of brominated mono-methano[60]fullerene malonate derivatives (two diads and one triad) are investigated for intramolecular and external heavy-atom effects on their fluorescence. Significant internal and external heavy-atom effects are observed in the three cases. It is shown that the internal effect doubles when going from the diads to the triad. In bromobenzene and in iodobenzene, the external effect is predominant, and diads and triad behave identically.

Time-resolved fluorescence study of human recombinant interferon alpha 2. Association state of the protein, spatial proximity of the two tryptophan residues.

Human recombinant interferon alpha 2 belongs a to family of proteins active against a wide range of viruses. It contains two tryptophan residues located at positions 77 and 141 in the peptide sequence. The fluorescence emission spectrum of these tryptophan residues displays a maximum at 335 nm. The fluorescence intensity decay is described by one broad excited-state-lifetime population centered around a value of 1.7 ns (full width at half maximum, 1.5 ns). These observations suggest that in the native protein, both tryptophan residues emit from similar environments, not directly exposed to the surrounding solvent. The anisotropy decay is essentially biexponential. The correlation-time value characterizing the Brownian rotation of the protein varies linearly with the viscosity/temperature ratio. The calculated hydrodynamic volumes are compatible with the existence of a dimer and a tetramer, at pH 5.5 and 9.4, respectively. Addition of urea at pH 5.5 disrupts the dimer and modifies to some extent the excited-state-lifetime distribution which becomes more heterogeneous. Disulfide-bond reduction also dissociates the dimer and leads to a highly heterogeneous fluorescence-intensity decay with four excited-state-lifetime populations. An opening of the local structure in the Trp region of the protein is likely to occur in these conditions. The fast-anisotropy-decay components can be due to either fast rotation or energy transfer between the indoles. Close proximity of the two Trp residues (less than 1 nm) is suggested from steady-state and time-resolved fluorescence-anisotropy measurements in vitrified medium [95% (by mass) glycerol at -38 degrees C]. This suggestion is in agreement with the recently published three-dimensional structure of the homologous protein murine interferon beta [Senda, T., Shimazu, T., Matsuda, S. Kawano, G., Shimizu, H., Nakamura, K. T. & Mitsui, Y. (1992) EMBO J. 11, 3193-3201].

Dibucaine interaction with phospholipid vesicles. A resonance energy-transfer study.

Resonance energy transfer between a local anaesthetic, dibucaine (donor) and a set of functionalized probes [n-(9-anthroyloxy)stearic acids, n = 2, 3, 6, 7, 9 and 12 and 16-(9-anthroyloxy)palmitic acid] (acceptors) was found to be an efficient process with a critical radius of transfer Ro = 2.1 nm, this interaction being used to locate the drug in a model membrane system, small unilamellar vesicles of dipalmitoylglycerophosphocholine, both above and below the temperature of the gel-to-the-liquid-crystal transition of the phospholipid. From the sequence of relative quenching efficiencies of dibucaine fluorescence upon incorporation of the probes, it was concluded that the drug intercalates in the membrane near the glycerol backbone of the lipid. In addition, it was found that dibucaine location is not significantly affected upon crossing the phase-transition temperature of the phospholipid. Dibucaine photophysics was also studied and the short lifetime of the neutral form of the anaesthetic with respect to that of the monoprotonated species was attributed to an intramolecular charge-transfer interaction. From the study of its partition coefficient between the membrane and the aqueous phase, it was concluded that the only significant species present in the membrane is the charged one.