A three-state model for the photophysics of guanine

The nonadiabatic photochemistry of the guanine molecule (2-amino-6-oxopurine) and some of its tautomers has been studied by means of the high-level theoretical ab initio quantum chemistry methods CASSCF and CASPT2. Accurate computations, based by the first time on minimum energy reaction paths, states minima, transition states, reaction barriers, and conical intersections on the potential energy hypersurfaces of the molecules lead to interpret the photochemistry of guanine and derivatives within a three-state model. As in the other purine DNA nucleobase, adenine, the ultrafast subpicosecond fluorescence decay measured in guanine is attributed to the barrierless character of the path leading from the initially populated (1)(pi pi* L-a) spectroscopic state of the molecule toward the low-lying methanamine-like conical intersection (gs/pi pi* L-a)(CI). On the contrary, other tautomers are shown to have a reaction energy barrier along the main relaxation profile. A second, slower decay is attributed to a path involving switches toward two other states, (1)(pi pi* L-b) and, in particular, (1)(n(o)pi*), ultimately leading to conical intersections with the ground state. A common framework for the ultrafast relaxation of the natural nucleobases is obtained in which the predominant role of a pi pi*-type state is confirmed.

Up-converter nanophosphor Y2O2S:Er,Yb aminofunctionalized containing or not spherical silica conjugated with BSA

This work reports on the study of the nanophosphor. Y2O2S:Er(2%),Yb(1%) obtained from polymeric resin to be evaluated as fluorescent label with Suitable features to conjugate with bio-molecules for bioassay up-converting phosphor technology (UPT) application A conjugation protocol between bovine serum albumin (BSA) and the aminofunctionalized nanophosphor containing or not spherical silica was established UV-vis results indicated an effective conjugation between nanophosphor particles and the protein up-conversion measurements under 980 nm excitation performed for samples before and after aminofunctionalization showed that nanophosphor particles luminescence features keep unchanged in all cases All results suggest that the adapted protocol is feasible to provide a nanoparticle-protein effective conjugation preserving nanophosphor optical features The presence of spherical silica can be considered advantageous to increase conjugation efficiency Therefore. the developed procedure is applicable for future conjugations between the chosen nanophosphor and the streptavidin protein chat takes part in the well known self-recognition system avidin-biotin. (C) 2009 Elsevier B.V All rights reserved.

Yttrium oxysulfide nanosized spherical particles doped with Yb and Er or Yb and Tm: efficient materials for up-converting phosphor technology field

This work reports on the preparation, structural and luminescent studies of nanosized up-converter phosphors Y2O2S:Yb(4%), Er(0.1%) and Y2O2S:Yb(4%), Tm(0.1%),both from polymeric and basic carbonate precursors. The precursors were submitted to a sulphuration process that was previously developed for oxysulfide preparation from basic carbonate. From XRD data, all phosphors presented the oxysulfide phase and the mean crystallite size estimated from the Scherrer formula in the range of 15-20 nm. Polymeric precursor leads to the smallest crystallite size independent on the doping ion. SEM and TEM results confirmed that basic carbonate leads to spherical particles with narrow size distribution and mean diameter of 150 nm, and polymeric precursor smaller spherical particles with diameter between 20 and 40 nm. Up-conversion studies under 980 nm laser excitation showed that Er-doped phosphors present strong green emission related to H-2(11/2), S-4(3/2) --> I-4(15/2) Er transitions as well as the red ones, F-4(9/2) --> I-4(15/2). Tm-doped samples show strong blue emission assigned to (1)G(4) --> H-3(6) and also the red ones, related to (1)G(4) --> F-3(4). Therefore, the sulphuration method was successfully applied to prepare nanosized and nanostructured blue and green up-converter oxysulfide phosphors starting from basic carbonate and polymeric precursors. (C) 2003 Elsevier B.V. All rights reserved.

Optical properties and energy transfer processes in (Tm3+, Nd3+) doped tungstate fluorophosphate glass

We investigate the linear optical properties and energy transfer processes in tungstate fluorophosphate glass doped with thulium (Tm3+) and neodymium (Nd3+) ions. The linear absorption spectra from 370 to 3000 nm were obtained. Transitions probabilities, radiative lifetimes, and transition branching ratios were determined using the Judd-Ofelt [Phys. Rev. 127, 750 (1962); J. Chem. Phys. 37, 511 (1962)] theory. Frequency up-conversion to the blue region and fluorescence in the infrared were observed upon pulsed excitation in the range of 630-700 nm. The excitation spectra of the luminescence were obtained to understand the origin of the signals. The temporal decay of the fluorescence was measured for different concentrations of the doping ions. Energy transfer rates among the Tm3+ and Nd3+ ions were also determined.

Morphological and luminescent studies on nanosized Er, Yb-Yttrium oxide up-converter prepared from different precursors

In this paper, we report luminescent and morphological studies with yttrium oxide samples doped with ytterbium and erbium. The samples were prepared by the combustion method and also from different precursors: oxalate, basic carbonate and polymeric resin. All powders were identified Lis being an yttrium oxide with a C-form structure, independent of the employed precursor. From mean crystallite size measurements, it was verified that oxides prepared through the polymeric precursor and combustion methods lead to the smallest crystallite size. Particle shape and size were investigated by SEM and TEM, and showed that both the oxalate precursor and the combustion methods do not provide oxide materials of suitable shape or size, on the other hand. The basic carbonate and polymeric precursors resulted in spherically shaped particles with an average diameter of 90 and 15 run. respectively, Upon 980 run diode laser excitation, green and red emission lines were detected for all samples and were assigned to the H-2(11/2) S-4(3/2) -> I-4(15/2) and (4)Fg(9/2) -> 4I(15/12) transitions, respectively. Such transitions are characteristic for Er3+ and result from energy transfer from Yb3+ energy levels, F-2(7/2) -> F-2(5/2). A relationship between the decrease in the mean crystallite size and the enhancement in red emission was also established as well as the influence of the presence of a high percentage of Yb-3 Both factors promote ET from Yb3+ (F-2(5/2)) to Er3+ (I-4(11/2)). (c) 2004 Elsevier B.V. All rights reserved.

Energy transfer assisted frequency upconversion in Ho 3+ doped fluoroindate glass

Experimental results are reported which show a strong evidence of energy transfer between Ho 3+ ions in a fluoroindate glass excited by a pulsed laser operating at 640 nm. We identified the origin of the blue and green upconverted fluorescence observed as being due to a Ho 3+-Ho 3+ pair interaction process. The dynamics of the fluorescence revealed the pathways involved in the energy transfer assisted upconversion process. © 2002 American Institute of Physics.

Frequency upconversion involving triads and quartets of ions in a Pr3+/Nd3+ codoped fluoroindate glass

Frequency upconversion (UC) processes involving energy transfer (ET) among Nd 3+ and Pr 3+ ions in a fluoroindate glass are reported. In a first experiment, the excitation of Pr 3+ [transition 3H 4→ 1D 2] and of Nd 3+ [transition 4I 9/2→( 2G 7/2+ 4G 5/2)] was achieved with a dye laser operating in the 575-590 nm range. In a second experiment, the Nd 3+ ions were excited with the second harmonic of a Nd: YAG laser at 532 nm. The ET processes leading to UC in both experiments were studied by monitoring the blue fluorescence decay at 480 nm due to the transition 3P 0→ 3H 4 in Pr 3+. In the more relevant UC process, quartets of ions (Nd-Nd-Pr-Pr) are excited due to absorption of three laser photons by two Nd 3+ ions which transfer their energy to two Pr 3+ ions. Each Pr 3+ ion promoted to the 3P 0 level decays to the ground state emitting one photon in the blue region. This conclusion was achieved investigating the dependence of the UC fluorescence intensity as a function of laser intensity, samples concentrations, and temporal behavior of the UC signal. Other UC processes involving nonisoionic groups of three ions are also reported. © 2002 American Institute of Physics.

Ultrafast Relaxation Dynamics of Osmium-Polypyridine Complexes in Solution

We present steady-state absorption and emission spectroscopy and femtosecond broadband photoluminescence up-conversion spectroscopy studies of the electronic relaxation of Os(dmbp)3 (Os1) and Os(bpy)2(dpp) (Os2) in ethanol, where dmbp is 4,4′-dimethyl-2,2′-biypridine, bpy is 2,2′-biypridine, and dpp is 2,3-dipyridyl pyrazine. In both cases, the steady-state phosphorescence is due to the lowest 3MLCT state, whose quantum yield we estimate to be ≤5.0 × 10–3. For Os1, the steady-state phosphorescence lifetime is 25 ns. In both complexes, the photoluminescence excitation spectra map the absorption spectrum, pointing to an excitation wavelength-independent quantum yield. The ultrafast studies revealed a short-lived (≤100 fs) fluorescence, which stems from the lowest singlet metal-to-ligand-charge-transfer (1MLCT) state and decays by intersystem crossing to the manifold of 3MLCT states. In addition, Os1 exhibits a 50 ps lived emission from an intermediate triplet state at an energy 2000 cm–1 above that of the long-lived (25 ns) phosphorescence. In Os2, the 1MLCT–3MLCT intersystem crossing is faster than that in Os1, and no emission from triplet states is observed other than the lowest one. These observations are attributed to a higher density of states or a smaller energy spacing between them compared with Os1. They highlight the importance of the energetics on the rate of intersystem crossing.

Preparation and characterization of stable aqueous suspensions of up-converting Er3+/Yb3+-doped LiNbO3 nanocrystals

The preparation of LiNbO3:Er3+/Yb3+ nanocrystals and their up-conversion properties have been studied. It is demonstrated that polyethyleneimine- (PEI) assisted dispersion procedures allow obtaining stable aqueous LiNbO3:Er3+/Yb3+ powder suspensions, with average size particles well below the micron range (100–200 nm) and the isoelectric point of the suspension reaching values well above pH 7. After excitation of Yb3+ ions at a wavelength of 980 nm, the suspensions exhibit efficient, and stable, IR-to-visible (green and red) up-conversion properties, easily observed by the naked eye, very similar to those of the starting crystalline bulk material.

Condensed-phase optical refrigeration

We review progress on laser cooling of solids. The general process that enables cooling to occur is based on anti-Stokes fluorescence. Candidate materials for laser cooling are discussed, including gases, dyes, crystals, semiconductors, and ionically doped glasses. Cooling processes and necessary conditions for cooling are outlined, and general thermodynamic limitations are discussed. This is followed by a more detailed discussion of one specific material, ytterbium-doped ZBLAN, with consideration given to optimization of the laser cooling process and applications. (C) 2003 Optical Society of America.

Ultrahigh step-up dc-dc converter for distributed generation by three Degrees of Freedom (3DoF) approach

This paper proposes a novel dc-dc converter topology to achieve an ultrahigh step-up ratio while maintaining a high conversion efficiency. It adopts a three degree of freedom approach in the circuit design. It also demonstrates the flexibility of the proposed converter to combine with the features of modularity, electrical isolation, soft-switching, low voltage stress on switching devices, and is thus considered to be an improved topology over traditional dc-dc converters. New control strategies including the two-section output voltage control and cell idle control are also developed to improve the converter performance. With the cell idle control, the secondary winding inductance of the idle module is bypassed to decrease its power loss. A 400-W dc-dc converter is prototyped and tested to verify the proposed techniques, in addition to a simulation study. The step-up conversion ratio can reach 1:14 with a peak efficiency of 94% and the proposed techniques can be applied to a wide range of high voltage and high power distributed generation and dc power transmission.

Enhanced luminescence of Tb(3+)/Eu(3+) doped tellurium oxide glass containing silver nanostructures

We report on energy transfer studies in terbium (Tb(3+))-europium (Eu(3+)) doped TeO(2)-ZnO-Na(2)O-PbO glass containing silver nanostructures. The samples excitation was made using ultraviolet radiation at 355 nm. Luminescence spectra were recorded from approximate to 480 to approximate to 700 nm. Enhanced Eu(3+) luminescence at approximate to 590 nm (transition (5)D(0)-(7)F(1)) and approximate to 614 nm (transition (5)D(0)-(7)F(2)) are observed. The large luminescence enhancement was obtained due to the simultaneous contribution of the Tb(3+)-Eu(3+) energy transfer and the contribution of the intensified local field on the Eu(3+) ions located near silver nanostructures.

Luminescence of Tb(3+) doped TeO(2)-ZnO-Na(2)O-PbO glasses containing silver nanoparticles

Luminescence properties of Tb(3+) doped TeO(2)-ZnO-Na(2)O-PbO glasses containing silver nanoparticles (NPs) were investigated. The absorption band due to the surface plasmon resonance in the NPs was observed. Its amplitude increases with the heat treatment of the samples that controls the nucleation of the NPs. Tb(3+) emission bands centered at approximate to 485, approximate to 550, approximate to 585, and approximate to 623 nm were detected for excitation at 377 nm. The whole spectrum is intensified by the appropriate annealing time of the samples. Enhancement by approximate to 200% of the Tb(3+) luminescence at 550 nm was observed for samples annealed at 270 degrees C during 62 h. This enhancement effect is due to the local field amplitude that increases with the amount of silver NPs and their aggregates. (C) 2008 American Institute of Physics. [DOI: 10.1063/1.3010867]

Influence of the heat treatment on the nucleation of silver nanoparticles in Tm(3+) doped PbO-GeO(2) glasses

Nucleation of silver nanoparticles (NPs) in Tm(3+) doped PbO-GeO(2) (PGO) glass is reported. The influence of the heat treatment on the nucleation of silver NPs is studied by means of transmission electron microscopy and optical spectroscopy. Two heat treatment procedures were applied in order to compare their performance. Observation of infrared-to-visible frequency upconversion (UC) luminescence of Tm(3+) ions is reported and correlated with the heat-treatment procedure. Enhancement of the UC emission for samples heat treated during various time intervals is attributed to the increased local field in the vicinity of the NPs. Quenching of the UC signal was also observed and correlated with the growth of NPs amount and size.

PbO-GeO(2) rib waveguides for photonic applications

This work presents for the first time to our knowledge the fabrication and characterization of rib waveguides produced with PbO-GeO(2) (PGO) thin films. The target was manufactured using pure oxides ( 60 PbO-40 GeO(2), in wt%) and amorphous thin films were produced with the RF sputtering technique. PGO thin films present small absorption in the visible and in the near infrared and refractive index of similar to 2.0. The definition of the rib waveguide structure was made using conventional optical lithography followed by plasma etching, performed in a Reactive Ion Etching (RIE) reactor. Light propagation mode in the waveguide structure was analyzed using integrated optic simulation software. Optical loss measurements were performed to determine the propagation loss at 633 nm, for ribs with height of 70 nm and width of 3-5 mu m; experimental values around 2 dB/cm were found for the propagation loss and confirmed the theoretical calculations. The results obtained demonstrate that PGO thin films are potential candidates for application in integrated optics. Published by Elsevier B.V.