A general threshold stress hybrid hazard model for lifetime data

In this paper we propose a hybrid hazard regression model with threshold stress which includes the proportional hazards and the accelerated failure time models as particular cases. To express the behavior of lifetimes the generalized-gamma distribution is assumed and an inverse power law model with a threshold stress is considered. For parameter estimation we develop a sampling-based posterior inference procedure based on Markov Chain Monte Carlo techniques. We assume proper but vague priors for the parameters of interest. A simulation study investigates the frequentist properties of the proposed estimators obtained under the assumption of vague priors. Further, some discussions on model selection criteria are given. The methodology is illustrated on simulated and real lifetime data set.

The search for a potentially new molecular species, SiAs: A theoretical contribution

Electronic states of a new molecular species, SiAs, correlating with the three lowest dissociation channels are characterized at a high-level of theory using the CASSCF/MRCI approach along with quintuple-xi quality basis sets. This characterization includes potential energy curves, vibrational energy levels, spectroscopic parameters, dipole and transition dipole moment functions, transition probabilities, and radiative lifetimes. For the ground state (X-2 Pi), an assessment of spin-orbit effects and the interaction with the close-lying A(2)Sigma(+) state is also reported. Similarities and differences with other isovalent species such as SiP and CAs are also discussed.

Experimental and Theoretical Study on the One- and Two-Photon Absorption Properties of Novel Organic Molecules Based on Phenylacetylene and Azoaromatic Moieties

This Article reports a combined experimental and theoretical analysis on the one and two-photon absorption properties of a novel class of organic molecules with a pi-conjugated backbone based on phenylacetylene (JCM874, FD43, and FD48) and azoaromatic (YB3p2S) moieties. Linear optical properties show that the phenylacetylene-based compounds exhibit strong molar absorptivity in the UV and high fluorescence quantum yield with lifetimes of approximately 2.0 ns, while the azoaromatic-compound has a strong absorption in the visible region with very low fluorescence quantum yield. The two-photon absorption was investigated employing nonlinear optical techniques and quantum chemical calculations based on the response functions formalism within the density functional theory framework. The experimental data revealed well-defined 2PA spectra with reasonable cross-section values in the visible and IR. Along the nonlinear spectra we observed two 2PA allowed bands, as well as the resonance enhancement effect due to the presence of one intermediate one-photon allowed state. Quantum chemical calculations revealed that the 2PA allowed bands correspond to transitions to states that are also one-photon allowed, indicating the relaxation of the electric-dipole selection rules. Moreover, using the theoretical results, we were able to interpret the experimental trends of the 2PA spectra. Finally, using a few-energy-level diagram, within the sum-over-essential states approach, we observed strong qualitative and quantitative correlation between experimental and theoretical results.

A theoretical contribution characterizing a potentially new molecular species: MgAs

A new molecular species, MgAs, is investigated theoretically for the first time at the CASSCF/MRCI level using quintuple-zeta quality basis sets. Potential energy curves for the lowest-lying electronic states are presented as well as the associated spectroscopic constants. Dipole and transition moment functions for selected states complement this characterization. Estimates of transition probabilities and radiative life-times for the most important transitions are also reported. The effect of spin-orbit interactions is clearly reflected on the potential energy curves. Comparisons with BeAs, BeN, and BeP are made where pertinent. (C) 2011 Elsevier B.V. All rights reserved.

Photoprotection and the Photophysics of Acylated Anthocyanins

The proposed role of anthocyanins in protecting plants against excess solar radiation is consistent with the occurrence of ultrafast (525 ps) excited-state proton transfer as the major de-excitation pathway of these molecules. However, because natural anthocyanins absorb mainly in the visible region of the spectra, with only a narrow absorption band in the UV-B region, this highly efficient deactivation mechanism would essentially only protect the plant from visible light. On the other hand, ground-state charge-transfer complexes of anthocyanins with naturally occurring electron-donor co-pigments, such as hydroxylated flavones, flavonoids, and hydroxycinnamic or benzoic acids, do exhibit high UV-B absorptivities that complement that of the anthocyanins. In this work, we report a comparative study of the photophysics of the naturally occurring anthocyanin cyanin, intermolecular cyanincoumaric acid complexes, and an acylated anthocyanin, that is, cyanin with a pendant coumaric ester co-pigment. Both inter- and intramolecular anthocyaninco-pigment complexes are shown to have ultrafast energy dissipation pathways comparable to those of model flavylium cationco-pigment complexes. However, from the standpoint of photoprotection, the results indicate that the covalent attachment of co-pigment molecules to the anthocyanin represents a much more efficient strategy by providing the plant with significant UV-B absorption capacity and at the same time coupling this absorption to efficient energy dissipation pathways (ultrafast internal conversion of the complexed form and fast energy transfer from the excited co-pigment to the anthocyanin followed by adiabatic proton transfer) that avoid net photochemical damage.

Effect of the vanadium(V) concentration on the spectroscopic properties of nanosized europium-doped yttrium phosphates

Nanosized rare earth phosphovanadate phosphors (Y(P,V)O-4:Eu3+) have been prepared by applying the organic-inorganic polymeric precursors methodology. Luminescent powders with tetragonal structure and different vanadate concentrations (0%, 1%, 5%, 10%, 20%, 50%, and 100%, with regard to the phosphate content) were then obtained for evaluation of their structural and spectroscopic properties. The solids were characterized by scanning electron microscopy, X-ray diffractometry, vibrational spectroscopy (Raman and infrared), and electronic spectroscopy (emission, excitation, luminescence lifetimes, chromaticity, quantum efficiencies, and Judd-Ofelt intensity parameters). The solids exhibited very intense D-5(0) -> F-7(J) Eu3+ transitions, and it was possible to control the luminescent characteristics, such as excitation maximum, lifetime and emission colour, through the vanadium(V) concentration. The observed luminescent properties correlated to the characteristics of the chemical environments around the Eu3+ ions with respect to the composition of the phosphovanadates. The Eu3+ luminescence spectroscopy results indicated that the presence of larger vanadium(V) amounts in the phosphate host lattice led to more covalent and polarizable chemical environments. So, besides allowing for control of the luminescent properties of the solids, the variation in the vanadate concentration in the obtained YPO4:Eu3+ phosphors enabled the establishment of a strict correlation between the observable spectroscopic features and the chemical characteristics of the powders.

Effect of interaction with micelles on the excited-state optical properties of zinc porphyrins and J-aggregates formation

This work reports on the photophysical properties of zinc porphyrins meso-tetrakis methylpyridiniumyl (Zn2+TMPyP) and meso-tetrakis sulfonatophenyl (Zn2+TPPS) in homogeneous aqueous solutions and in the presence of sodium dodecyl sulfate (SDS) and cetyltrimethyl ammonium bromide (CTAB) micelles. The excited-state dynamic was investigated with the Z-scan technique, UV-Vis absorption, and fluorescence spectroscopy. Photophysical parameters were obtained by analyzing the experimental data with a conventional five-energy-level diagram. The interaction of the charged side porphyrin groups with oppositely charged surfactants can reduce the electrostatic repulsion between porphyrin molecules leading to aggregation, which affected the porphyrin characteristics such as absorption cross-sections, lifetimes and quantum yields. The interaction between anionic ZnTPPS with cationic CTAB micelles induced the formation of porphyrin J-aggregates, while this effect was not observed in the interaction of ZnTMPyP with SDS micelles. This difference is, probably, due to the difference in electrostatic repulsion between the porphyrin molecules. The insights obtained by these results are important for the understanding of the photophysical behavior of porphyrins, regarding potential applications in pharmacokinetics as encapsulation of photosensitizer for drug delivery systems and in its interaction with cellular membrane.