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Excitation Spectra (excitation + spectrum)
Selected AbstractsThe Influence of Alkyl-Chain Length on Beta-Phase Formation in PolyfluorenesADVANCED FUNCTIONAL MATERIALS, Issue 1 2009Daniel W. Bright Abstract Di- n -alkyl substituted polyfluorenes with alkyl chain lengths of 6, 7, 8, 9, and 10 carbon atoms (PF6, PF7, PF8, PF9, and PF10) are studied in dilute solution in MCH using optical spectroscopy. Beta-phase is formed upon cooling in solutions (, 7,µg mL,1) of PF7, PF8, and PF9 only, which is observed as an equilibrium absorption peak at , 437,nm and strong changes in the emission spectra. Beta-phase is formed upon thermal cycling to low temperature in solutions (,7,µg mL,1) of PF7, PF8, and PF9, which is observed as an equilibrium absorption peak at , 437,nm and strong changes in the emission spectra. Beta phase is found to occur more favorably in PF8 than in PF7 or PF9, which is attributed to a balance between two factors. The first is the dimer/aggregate formation efficiency, which is poorer for longer (more disordered) alkyl chain lengths, and the second is the Van der Waals bond energy available to overcome the steric repulsion and planarize the conjugated backbone, which is insufficient in the PF6 with a shorter alkyl chain. Beta phase formation is shown to be a result of aggregation, not a precursor to it. A tentative value of the energy required to planarize the fluorene backbone of (15.6,±,2.5) kJ mol,1 monomer is suggested. Excitation spectra of PF6, PF7, PF8, and PF9 in extremely dilute (, 10,ng mL,1) solution show that beta phase can form reversibly in dilute solutions of PF7, PF8 and PF9, which is believed to be a result of chain collapse or well dispersed aggregates being present in solution from dilution of more concentrated solutions. PF7, PF8, and PF9 also form beta phase in thermally cycled solid films spin-cast from MCH. However, in the films the PF7 formed a larger fraction of beta phase than the PF9, in contrast to the case in solutions, because it is less likely that the close-packed chains in the solid state will allow the formation of planarized chains with the longer PF9 side chains. [source] Photophysical and Photochemical Studies of PyridoxamineHELVETICA CHIMICA ACTA, Issue 10 2003Claudio Bueno The absorption and fluorescence emission of pyridoxamine were studied as function of pH and solvent properties. In the ground state, pyridoxamine exhibits different protonated forms in the range of pH,1.5,12. Fluorescence studies showed that the same species exist at the lowest singlet excited state but at different pH ranges. The phenol group is by ca. 8,units more acidic in the excited state than in the ground state. On the other hand, the pyridine N-atom is slightly more basic in the lowest excited state than in the ground state. Excitation spectra and emission decays in the pH range of 8,10 indicate the protonation of the pyridine N-atom by proton transfer from the amine group, in the ground and singlet excited states. Spectroscopic studies in different solvents showed that pyridoxamine in the ground or excited states exhibits intramolecular proton transfer from the pyridine N-atom to the phenol group, which is more favorable in solvents of low hydrogen-bonding capacity. The cationic form with the protonated phenolic group, which emits at shorter wavelength, is the dominant species in nonprotic solvents, but, in strong proton-donor solvents, both forms exist. The fluorescence spectra of these species exhibit blue shift in protic solvents. These shifts are well-correlated with the polarity and the H-donor ability of the solvent. [source] Development and application of an excitation ratiometric optical pH sensor for bioprocess monitoringBIOTECHNOLOGY PROGRESS, Issue 6 2008Ramachandram Badugu Abstract The development of a fluorescent excitation ratiometric pH sensor (AHQ-PEG) using a novel allylhydroxyquinolinium (AHQ) derivative copolymerized with polyethylene glycol dimethacrylate (PEG) is described. The AHQ-PEG sensor film is shown to be suitable for real-time, noninvasive, continuous, online pH monitoring of bioprocesses. Optical ratiometric measurements are generally more reliable, robust, inexpensive, and insensitive to experimental errors such as fluctuations in the source intensity and fluorophore photobleaching. The sensor AHQ-PEG in deionized water was shown to exhibit two excitation maxima at 375 and 425 nm with a single emission peak at 520 nm. Excitation spectra of AHQ-PEG show a decrease in emission at the 360 nm excitation and an increase at the 420 nm excitation with increasing pH. Accordingly, the ratio of emission at 420:360 nm excitation showed a maximum change between pH 5 and 8 with an apparent pKa of 6.40. The low pKa value is suitable for monitoring the fermentation of most industrially important microorganisms. Additionally, the AHQ-PEG sensor was shown to have minimal sensitivity to ionic strength and temperature. Because AHQ is covalently attached to PEG, the film shows no probe leaching and is sterilizable by steam and alcohol. It shows rapid (,2 min) and reversible response to pH over many cycles without any photobleaching. Subsequently, the AHQ-PEG sensor film was tested for its suitability in monitoring the pH of S. cereviseae (yeast) fermentation. The observed pH using AHQ-PEG film is in agreement with a conventional glass pH electrode. However, unlike the glass electrode, the present sensor is easily adaptable to noninvasive monitoring of sterilized, closed bioprocess environments without the awkward wire connections that electrodes require. In addition, the AHQ-PEG sensor is easily miniaturized to fit in microwell plates and microbioreactors for high-throughput cell culture applications. [source] Synthesis of Symmetrical Multichromophoric Bodipy Dyes and Their Facile Transformation into Energy Transfer Cassettes,CHEMISTRY - A EUROPEAN JOURNAL, Issue 21 2010Altan Bozdemir Dr. Abstract Multichromophoric boron-dipyrromethene (Bodipy) dyes synthesized on phenylene-ethynylene platforms have been be converted to energy transfer cassettes in a one-step chemical transformation. Excitation energy transfer processes in these highly symmetrical derivatives were studied in detail, including time-resolved fluorescence spectroscopy techniques. Excitation spectra and the emission lifetimes suggest efficient energy transfer between the donor and acceptor chromophore. These novel energy transfer cassettes, while highlighting a short-cut approach to similar energy transfer systems, could be useful as large pseudo-Stokes shift multichromophoric dyes with potential applications in diverse applications. Fenilenetilen platformu üzerinde sentezlenen multikromoforik Bodipy boyarmaddeleri, tek basamakl, bir kimyasal transformasyonla enerji transferi kasetlerine dönü,türülmü,tür. Zaman ayr,ml, floresans spektroskopisi tekniklerinin de içinde bulundu,u yöntemlerle, yüksek simetri ö,eleri bulunduran bu türevlerdeki eksitasyon enerjisi transferi süreçleri ayr,nt,l, olarak çal,,,lm,,t,r. Eksitasyon spektrumlar, ve emisyon ömürlerindeki de,i,im, donör ve akseptör kromoforlar, aras,nda etkin bir enerji transferi oldu,unu dü,ündürmektedir. Bu yeni enerji transfer kasetleri, benzer enerji transfer sistemlerine kolay bir geçi, yolu göstermekle birlikte, pek çok farkl, alanda potansiyel uygulamalar, olabilecek, büyük pseudo-Stokes kaymas, de,erlerine sahip multikromoforik boyarmaddeler olarak da yararl, olabilirler. [source] Harvesting Excitons Via Two Parallel Channels for Efficient White Organic LEDs with Nearly 100% Internal Quantum Efficiency: Fabrication and Emission-Mechanism AnalysisADVANCED FUNCTIONAL MATERIALS, Issue 1 2009Qi Wang Abstract By incorporating two phosphorescent dyes, namely, iridium(III)[bis(4,6-difluorophenyl)-pyridinato-N,C2,]picolinate (FIrpic) for blue emission and bis(2-(9,9-diethyl-9H -fluoren-2-yl)-1-phenyl-1H -benzoimidazol-N,C3)iridium(acetylacetonate) ((fbi)2Ir(acac)) for orange emission, into a single-energy well-like emissive layer, an extremely high-efficiency white organic light-emitting diode (WOLED) with excellent color stability is demonstrated. This device can achieve a peak forward-viewing power efficiency of 42.5,lm,W,1, corresponding to an external quantum efficiency (EQE) of 19.3% and a current efficiency of 52.8,cd,A,1. Systematic studies of the dopants, host and dopant-doped host films in terms of photophysical properties (including absorption, photoluminescence, and excitation spectra), transient photoluminescence, current density,voltage characteristics, and temperature-dependent electroluminescence spectra are subsequently performed, from which it is concluded that the emission natures of FIrpic and (fbi)2Ir(acac) are, respectively, host,guest energy transfer and a direct exciton formation process. These two parallel pathways serve to channel the overall excitons to both dopants, greatly reducing unfavorable energy losses. It is noteworthy that the introduction of the multifunctional orange dopant (fbi)2Ir(acac) (serving as either hole-trapping site or electron-transporting channel) is essential to this concept as it can make an improved charge balance and broaden the recombination zone. Based on this unique working model, detailed studies of the slight color-shift in this WOLED are performed. It is quantitatively proven that the competition between hole trapping on orange-dopant sites and undisturbed hole transport across the emissive layer is the actual reason. Furthermore, a calculation of the fraction of trapped holes on (fbi)2Ir(acac) sites with voltage shows that the hole-trapping effect of the orange dopant is decreased with increasing drive voltage, leading to a reduction of orange emission. [source] Minocycline-Based Europium(III) Chelate Complexes: Synthesis, Luminescent Properties, and Labeling to StreptavidinHELVETICA CHIMICA ACTA, Issue 11 2009Takuya Nishioka Abstract Two chelate ligands for europium(III) having minocycline (=(4S,4aS,5aR,12aS)-4,7-bis(dimethylamino)-1,4,4a,5,5a,6,11,12a-octahydro-3,10,12,12a-tetrahydroxy-1,11-dioxonaphthacene-2-carboxamide; 5) as a VIS-light-absorbing group were synthesized as possible VIS-light-excitable stable Eu3+ complexes for protein labeling. The 9-amino derivative 7 of minocycline was treated with H6TTHA (=triethylenetetraminehexaacetic acid=3,6,9,12-tetrakis(carboxymethyl)-3,6,9,12-tetraazatetradecanedioic acid) or H5DTPA (=diethylenetriaminepentaacetic acid=N,N -bis{2-[bis(carboxymethyl)amino]ethyl}glycine) to link the polycarboxylic acids to minocycline. One of the Eu3+ chelates, [Eu3+(minocycline-TTHA)] (13), is moderately luminescent in H2O by excitation at 395,nm, whereas [Eu3+(minocycline-DTPA)] (9) was not luminescent by excitation at the same wavelength. The luminescence and the excitation spectra of [Eu3+(minocycline-TTHA)] (13) showed that, different from other luminescent EuIII chelate complexes, the emission at 615,nm is caused via direct excitation of the Eu3+ ion, and the chelate ligand is not involved in the excitation of Eu3+. However, the ligand seems to act for the prevention of quenching of the Eu3+ emission by H2O. The fact that the excitation spectrum of [Eu3+(minocycline-TTHA)] is almost identical with the absorption spectrum of Eu3+ aqua ion supports such an excitation mechanism. The high stability of the complexes of [Eu3+(minocycline-DTPA)] (9) and [Eu3+(minocycline-TTHA)] (13) was confirmed by UV-absorption semi-quantitative titrations of H4(minocycline-DTPA) (8) and H5(minocycline-TTHA) (12) with Eu3+. The titrations suggested also that an 1,:,1 ligand Eu3+ complex is formed from 12, whereas an 1,:,2 complex was formed from 8 minocycline-DTPA. The H5(minocycline-TTHA) (12) was successfully conjugated to streptavidin (SA) (Scheme,5), and thus the applicability of the corresponding Eu3+ complex to label a protein was established. [source] Features of fluorescence spectra of polyethylene 2,6-naphthalate films,JOURNAL OF APPLIED POLYMER SCIENCE, Issue 1 2007I. Ouchi Abstract The characteristics of the fluorescence spectra of polyethylene 2,6-naphthalate (PEN) films were compared with those of poly(ethylene terephthalate) (PET). The fluorescence spectra of PEN films were found, by photoselection, to consist of two components, one peaking at 425 nm and the other at 445 nm, with their emission transition moments perpendicular to each other. The integrated excitation spectra of the PEN films were much more intense than those of PET. After the resolution of the integrated excitation spectra of PEN, most, but not all, of their component peaks corresponded to those of the absorption spectra. On the basis of this fact together with previous data on photodegradation, the spectral component peaking at 445 nm originated, at least partly, from traces of photochemical products generated by exposure during the measurements. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 105: 114,121, 2007 [source] Study of electronic spectra of free-base porphin and Mg-porphin: Comprehensive comparison of variety of ab initio, DFT, and semiempirical methodsJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 3 2005Josef Abstract SAC (symmetry adapted cluster)/SAC-CI and CASPT2 (multiconfigurational second-order perturbation theory) electron excitation spectra of free-base porphin and magnesium-porphin were determined using basis set functions augmented by both the polarization and diffuse functions,6-31+G(d). Such basis is recommended for correct description of the spectra because diffuse functions play fundamental roles in the formation of Rydberg MOs. The obtained results indicated that already the lowest roots in Au, B1u, B2g, and B3g irreducible representations display Rydberg character. The calculated spectra are in a good agreement with both experimental and recently calculated electronic transitions. It is concluded that the SAC/SAC-CI level spectral lines are significantly affected by configuration selection when energy thresholds 5.0 × 10,6 and 5.0 × 10,7 a.u. are used for the determination of ground and excited state properties. © 2004 Wiley Periodicals, Inc. J Comput Chem 26: 294,303, 2005 [source] Acid-labile, thermoresponsive (meth)acrylamide polymers with pendant cyclic acetal moietiesJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 13 2008Xiao-Nan Huang Abstract Acid-labile, thermoresponsive polymers with pendant six-membered cyclic acetal groups were prepared by radical polymerization of two monomers, N -(2,2-dimethyl-1,3-dioxan-5-yl) methacrylamide (NDMM) and N -(2,2-dimethyl-1,3-dioxan-5-yl) acrylamide (NDMA). The aqueous solution properties of the polymers, PNDMM and PNDMA, were studied by turbidimetry, 1H NMR, fluorescence, and DSC measurements. It is found that both polymers show sensitive and reversible phase transitions with distinct lower critical solution temperatures (LCST). Below their LCSTs, there are still some polymer aggregates as evidenced by measurements of pyrene excitation spectra and urea effects on the cloud points (CP) of polymers. The salting effect of six inorganic sodium salts on the phase transition behavior of PNDMM was investigated by turbidimetric approach. The salting-out to salting-in effect is in the order of SO42, > F, > Cl, > Br, > I, > SCN,, following the Hofmeister's series. pH-dependent hydrolysis of PNDMM and PNDMA was studied by turbidimetric and 1H NMR methods. They are both pH-sensitive and their hydrolysis rates significantly increase with decreasing pH value. The CP of PNDMM gradually increases with the acid-triggered hydrolysis of the acetal groups and the hydrolyzed polymer with , 30% hydrolysis degree does not show thermally induced phase transition. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4332,4343, 2008 [source] Preparation and Photoluminescence Properties of Novel Color-Tunable MgY4Si3O13:Ce3+, Tb3+ Phosphors for Ultraviolet Light-Emitting DiodesJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 7 2010Hau-Yun Chung Oxide-based phosphors MgY4Si3O13 codoped with Ce3+ and Tb3+ were prepared in this study. Broad Ce3+ excitation spectra with the highest intensity at 330 nm were found for MgY4Si3O13:Ce3+, Tb3+ phosphors. Emission lines ranging from 450 to 650 nm originated from the 5D4,7FJ (J=6, 5, 4, 3) transitions of Tb3+ ions. The energy transfer from Ce3+ to Tb3+ occurred effectively in MgY4Si3O13:Ce3+, Tb3+ with a dipole,quadrupole interaction. Codoping Ce3+ with Tb3+ significantly increased the emission intensity of the prepared phosphors. Increasing the Tb3+ concentration led to the chromaticity coordinates of the prepared samples greatly shifting from the blue to the green region, extending the applicability of MgY4Si3O13:Ce3+, Tb3+ phosphors in solid-state lighting. [source] Performance characteristics according to Commission Decision 2002/657/EC in the fluorimetric determination of tetracycline in the absence and in the presence of magnesiumLUMINESCENCE: THE JOURNAL OF BIOLOGICAL AND CHEMICAL LUMINESCENCE, Issue 6 2007Noelia Rodríguez Abstract The fluorimetric determination of tetracycline is usually carried out in the presence of some metals that, through the formation of a complex with this antibiotic, enhance its fluorescence emission, giving more sensitive determination methods. It is well established that magnesium is one of these metals. However, it is possible that higher signals do not mean a real improvement in the quality of the analytical method. In this work, the univariate and multivariate fluorescence determination of tetracycline is performed in the presence and absence of Mg2+, comparing the quality of the analyses through some performance characteristics that, according to Commission Decision 2002/657/EC define the functional qualities of analytical methods. The methods with the best performance characteristics were multivariate determinations carried out in the absence of Mg2+, both when emission or excitation spectra were taken, the decision limits (CC,) being 13.1 and 20.1 µg/L and the detection capabilities (CC,) 25.3 and 38.5 µg/L, respectively. This study points out through a case study that higher analytical signals do not necessarily mean better performance characteristics of a method of analysis. Copyright © 2007 John Wiley & Sons, Ltd. [source] Photoactive Protochlorophyllide Regeneration in Cotyledons and Leaves from Higher Plants,,PHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 5 2000Benoît Schoefs ABSTRACT Chlorophyll accumulation during greening implies the continuous transformation of photoactive protochlorophyllide (Pchlide) to chlorophyllide. Since this reaction is a light-dependent step, the study of regeneration of photoactive Pchlide under a continuous illumination is difficult. Therefore this process is best studied on etiolated plants during a period of darkness following the initial photoreduction of photoactive Pchlide. In this study, the regeneration process has been studied using spinach cotyledons, as well as barley and bean leaves, illuminated by a single saturating flash. The regeneration was characterized using 77 K fluorescence emission and excitation spectra and high-performance liquid chromatography. The fluorescence data indicated that the same spectral forms of photoactive Pchlide are regenerated by different pathways: (1) photoactive Pchlide regeneration starts immediately after the photoreduction through the formation of a nonphotoactive Pchlide form, emitting fluorescence at approximately 651 nm. This form is similar to the large aggregate of photoactive Pchlide present before the illumination, but it contains oxidized form of nicotinamide adenine dinucleotide phosphate, instead of the reduced form (NADPH), in the ternary complexes; and (2) after the dislocation of the large aggregates of chlorophyllide,light-dependent NADPH:Pchlide a photooxidoreductase,NADPH ternary complexes, the regeneration occurs at the expense of the several nonphotoactive Pchlide spectral forms present before the illumination. [source] The Binding Characteristics and Intracellular Localization of Temoporfin (mTHPC) in Myeloid Leukemia Cells: Phototoxicity and Mitochondrial Damage,PHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 4 2000J. Y. Chen ABSTRACT The state of aggregation of the photosensitizer meso -tetrahydroxyphenylchlorin (mTHPC) in both cell free and intracellular environment was elucidated by comparing its absorption and excitation spectra. In methanol, mTHPC existed as monomers and strongly fluoresced. In aqueous solutions such as phosphate-buffered saline (PBS), mTHPC formed nonfluorescent aggregates. Some portion of mTHPC monomerized in the presence of 10% fetal calf serum PBS. In murine myeloid leukemia M1 and WEHI-3B (JCS) cells, cytoplasmic mTHPC were monomeric. By using organelle-specific fluorescent probes, it was found that mTHPC localized preferentially at the mitochondria and the perinuclear region. Photodynamic treatment of mTHPC-sensitized leukemia cells caused rapid appearance of the apoptogenic protein cytochrome c in the cytosol. Results from flow cytometric analysis showed that the release of cytochrome c was especially pronounced in JCS cells, and well correlated with the extent of apoptotic cell death as reported earlier. Electron microscopy revealed the loss of integrity of the mitochondrial membrane and the appearance of chromatin condensation as early as 1 h after light irradiation. We conclude that rapid release of cytochrome c from photodamaged mitochondria is responsible for the mTHPC-induced apoptosis in the myeloid leukemia JCS and M1 cells. [source] Green photoluminescence of SrGa2S4:Sn phosphorsPHYSICA STATUS SOLIDI (A) APPLICATIONS AND MATERIALS SCIENCE, Issue 11 2009Mutsumi Nagata Abstract The phosphor SrGa2S4:Sn exhibits a new green photoluminescence (PL) whose spectrum peaks at 534,nm. The phosphor also exhibits yellow and orange PL with very broad spectral bands when the excitation wavelength of the UV light is changed. These emissions are caused by the 5p,5s transition in the 5s2 configuration of Sn2+ ions occupying Sr2+ sites. The origin of the green emission was investigated by analyzing the PL excitation spectra and the electronic states of Sn2+ substituting at three different Sr2+ sites. The electronic states were analyzed in a first-principles calculation of the density of states. [source] Thermal quenching of luminescence and isovalent trap model for rare-earth-ion-doped AlNPHYSICA STATUS SOLIDI (B) BASIC SOLID STATE PHYSICS, Issue 6 2007H. J. Lozykowski Abstract Investigations of the luminescent properties of Pr-, Eu-, Tb- and Tm-implanted AlN thin films at temperature in the range 9,830 K are reported. The temperature studies of photoluminescence and cathodoluminescence spectra revealed unexpectedly weak thermal quenching for all investigated rare earth (RE) ions. The maximum CL emission is observed from Eu (red) at 485 K, Tb (green) at 590 K and Tm (blue) at 530 K, respectively. For Tb- and Tm-doped AlN samples, temperature-dependent crossrelaxation processes were observed. Photoluminescence excitation spectra, obtained under UV excitation in the spectral range 200,400 nm, exhibit several bands. It is proposed that the RE ions exist in semiconductors as isolated ions (singlet), nearest-neighbor (nn) ion pairs (dimer), and three ions (trimer). The Koster,Slater and simple spherical potential-well models for RE-structured isovalent (RESI) hole trap are proposed. The exciton binding energies of RESI traps are calculated and compared with experimental thermal-quenching energies. The energy-transfer processes between the AlN host and the 4f-shell systems are emphasized as the main mechanisms for thermal-quenching processes rather than nonradiative decay of 4f transitions. (© 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Two-photon photoluminescence and exciton binding energies in single-walled carbon nanotubesPHYSICA STATUS SOLIDI (B) BASIC SOLID STATE PHYSICS, Issue 10 2006R. Pomraenke Abstract We compare experimental one- and two-photon luminescence excitation spectra of single-walled carbon nanotubes at room temperature to ab initio calculations. The experimental spectra reveal a Rydberg-like series of excitonic states. The energy splitting between these states is a clear fingerprint of excitonic correlations in carbon nanotubes. From those spectra, we derive exciton binding energies of 0.3,0.4 eV for nanotubes with diameters between 6.8 Å and 9.0 Å. These energies are in quantitative agreement with our theoretical calculations, which predict the symmetries of the relevant excitonic wave functions and indicate that a low-lying optically dark excitonic state may be responsible for the low luminescence quantum yields in nanotubes. (© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Simple spin textures in a quantum dotPHYSICA STATUS SOLIDI (B) BASIC SOLID STATE PHYSICS, Issue 2 2003M. Ciorga Abstract Measurements and calculations previously reported for a lateral quantum dot at magnetic fields close to the transition to the maximum density droplet provided evidence that the increase of spin polarisation of a dot with magnetic field is interrupted by spin depolarization events. The loss of spin polarisation is associated with correlated states corresponding to condensation of spin excitons into spin textures. In this paper a detailed experimental and theoretical analysis is performed of the excitation spectra at the first two spin flip events in a few electron quantum dot. In this less complicated regime we are able to identify these correlated states as spin and charge excitons and bi-excitons. In particular we focus on a dot containing eight electrons. Coulomb blockade experiments, supported by detailed calculations, confirm the presence of these correlated states at the second spin flip. [source] Tunneling recombination processes in PbWO4 crystalsPHYSICA STATUS SOLIDI (C) - CURRENT TOPICS IN SOLID STATE PHYSICS, Issue 3 2007P. Fabeni Abstract Time-resolved emission and excitation spectra and luminescence decay kinetics were studied at 160-300 K for undoped and Mo-doped PbWO4 crystals under XeCl (4.02 eV), N2 (3.67 eV) and KrF (5.0 eV) pulsed excimer laser excitation. The G(II) emission was found to be responsible for the slow (µs-ms) luminescence decay. Under excitation or after irradiation in the exciton region (Eexc = 4.02 eV), this emission accompanies the monomolecular tunneling recombination in genetic pairs of electron and hole centers produced at the photo-thermally stimulated decay of localized excitons, which occurs without release of free charge carriers. Under excitation or after irradiation in the host lattice (Eexc = 5.0 eV) and defect-related (Eexc = 3.67 eV) regions, the bimolecular tunneling recombination takes place in chaotic pairs of the electron and hole centers created at the trapping of optically released free charge carriers. (© 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Light scattering in an electron-hole double quantum well in the presence of spin-orbit interactionPHYSICA STATUS SOLIDI (C) - CURRENT TOPICS IN SOLID STATE PHYSICS, Issue 2 2007C. H. Yang Abstract In this work, we study theoretically the lineshape and intensity of light scattering in an electron-hole double quantum well structure in the presence of spin-orbit interaction (SOI). Using the random phase approximation and Green function approach, the dispersion and the excitation spectra in this structure have been calculated. It is shown that scattering intensity can be tuned by the spin-orbit (SO) couple via the applied electrical field. The peaks shift as the polarization of electron or hole increases. (© 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Broadband spectrally dynamic solid state illumination sourcePHYSICA STATUS SOLIDI (C) - CURRENT TOPICS IN SOLID STATE PHYSICS, Issue 6 2006David B. Nicol Abstract Solid state lighting has done well recently in niche markets such as signage and displays, however, no available SSL technologies incorporate all the necessary attributes for general illumination. Development of a novel solid state general illumination source is discussed here. Two LEDs emitting at two distinct wavelengths can be monolithically grown and used to excite two or more phosphors with varied excitation spectra. The combined phosphorescence spectrum can then be controlled by adjusting the relative intensities of the two LED emissions. Preliminary phosphor analysis shows such a scheme to be viable for use in a spectrally dynamic broadband general illumination source. A tunnel junction is envisioned as a means of current spreading in a buried layer for three terminal operation. However, tunnel junction properties in GaN based materials are not well understood, and require further optimization to be practical devices. Preliminary results on GaN tunnel junctions are presented here as well. (© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Photoluminescence, Raman scattering and vertical transport of CdSe/CdMgSe superlatticesPHYSICA STATUS SOLIDI (C) - CURRENT TOPICS IN SOLID STATE PHYSICS, Issue 4 2006I. I. Reshina Abstract Photoluminescence and photoluminescence excitation spectra, vertical transport of photoexcited charge carriers and excitons and Raman scattering by optical phonons have been studied for the first time in low-strained superlattices CdSe/CdMgSe grown by molecular-beam epitaxy on InAs substrates. The vertical transport was studied by purely optical means involving an enlarged quantum well built into the superlattice. The enlarged quantum well served as a sink for the photoexcited carriers and excitons that have tunnelled through the superlattice. The measurements conducted in temperature range 2,150 K and also under in-plane strong magnetic fields show that vertical transport occurs mainly by free heavy-hole excitons but in superlattices with 5.9 nm and 7.3 nm periods it is not of the Bloch type. A comparison of the calculated energies of the interband transitions with the experimental data provides the valence-band ofsett in the range 0.4,0.5. The Raman spectra indicate a two-mode behavior of the optical phonons in CdMgSe barriers. (© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] UV light induced luminescence processes in AlN nanotips and ceramicsPHYSICA STATUS SOLIDI (C) - CURRENT TOPICS IN SOLID STATE PHYSICS, Issue 1 2005L. Trinkler Abstract UV induced luminescence properties of AlN (Eg = 6.2 eV) have been studied for AlN nanotips and AlN ceramics, using methods of photoluminescence, optically stimulated luminescence and thermoluminescence. In both types of objects the main luminescence band, which appears in prompt and stimulated emission spectra around 400 nm, arises due to presence of oxygen-related defects. The main difference between AlN nanotips and AlN ceramics is observed in excitation spectra and TL properties. Basing on the experimental results it is assumed that several different energy transfer mechanisms occur in AlN. (© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Fluorescence spectroscopy of H-ras transfected murine fibroblasts: A comparison with Monte Carlo simulationsBIOPOLYMERS, Issue 2 2010Shlomo Mark Abstract Autofluorescence properties of tissues have been widely used to diagnose various types of malignancies. In this study, we measured the autofluorescence properties of H-ras transfected murine fibroblasts and the counterpart control cells. The pair of cells is genetically identical except for the transfected H-ras gene. We applied Monte Carlo simulations to evaluate the relative contributions of Rayleigh and Mie scattering effects towards fluorescence in an in vitro model system of normal and H-ras transfected fibroblasts. The experimental results showed that fluorescence emission intensity was higher for normal cells than the malignant counterpart cells by about 30%. In normal cells, linearity in emission intensity was observed for cell densities of up to 1.0 × 106 cells/ml whereas for transformed cells it was up to 1.4 × 106 cells/ml. Nuclear volume changes give good account for the differences in the intrinsic fluorescence between normal and malignant cells. The Monte Carlo (MC) code, newly developed for this study, explains both predominant experimental features: the large fluorescence intensity differences between the transfected and the corresponding control cells as well as the phenomena of the red shift in the excitation spectra as a function of cell density. The contribution of Rayleigh scattering was found to be predominant compared to Mie scattering. © 2009 Wiley Periodicals, Inc. Biopolymers 93: 132,140, 2010. This article was originally published online as an accepted preprint. The "Published Online" date corresponds to the preprint version. You can request a copy of the preprint by emailing the Biopolymers editorial office at biopolymers@wiley.com [source] Electronic Energy Levels in all- trans Long Linear Polyenes: The Case of the 3,20-Di(tert -butyl)-2,2,21,21-tetramethyl-all- trans -3,5,7,9,11,13,15,17,19-docosanonaen (ttbp9) Conforming to Kasha's RuleCHEMISTRY - A EUROPEAN JOURNAL, Issue 13 2005Javier Catalán Prof. Dr. Abstract The absorption, fluorescence and fluorescence excitation spectra for 3,20-di(tert -butyl)-2,2,21,21-tetramethyl-all- trans -3,5,7,9,11,13,15,17,19-docosanonaen (ttbP9) in dilute solutions of 2-methylbutane were recorded at temperatures over the range 120,280 K. The high photostability of this nonaene allows us to assert that it exhibits a single fluorescence and that this can be unequivocally assigned to emission from its 11Bu excited state, it being the first excited electronic state. Available photophysical data for this polyene and the wealth of information reported for shorter all- trans polyenes allow us to conclude that if the first excited electronic state for the chromophore possessed 21Ag symmetry, then the energy of such a state might have been so close to that of the 11Bu state that: 1) the radiationless internal conversion mechanism would preclude the observation of the emission from the 11Bu state reported in this work and 2) the 21Ag state reached through internal conversion would be vibrationally coupled to 11Bu and would facilitate the detection of the emission from 21Ag, which was not observed in any of the solvents used in this work. The spectroscopic and photochemical implications of these findings for other polyenes are discussed. [source] Electronic and Vibrational Properties of Fluorenone in the Channels of Zeolite LCHEMISTRY - A EUROPEAN JOURNAL, Issue 10 2004André Devaux Dr. Abstract Fluorenone (C13H8O) was inserted into the channels of zeolite L by using gas-phase adsorption. The size, structure, and stability of fluorenone are well suited for studying host,guest interactions. The Fourier transform IR, Raman, luminescence, and excitation spectra, in addition to thermal analysis data, of fluorenone in solution and fluorenone/zeolite L are reported. Normal coordinate analysis of fluorenone was performed, based on which IR and Raman bands were assigned, and an experimental force field was determined. The vibrational spectra can be used for nondestructive quantitative analysis by comparing a characteristic dye band with a zeolite band that has been chosen as the internal standard. Molecular orbital calculations were performed to gain a better understanding of the electronic structure of the system and to support the interpretation of the electronic absorption and luminescence spectra. Fluorenone shows unusual luminescence behavior in that it emits from two states. The relative intensity of these two bands depends strongly on the environment and changes unexpectedly in response to temperature. In fluorenone/zeolite L, the intensity of the 300 nm band (lifetime 9 ,s) increases with decreasing temperature, while the opposite is true for the 400 nm band (lifetime 115 ,s). A model of the host,guest interaction is derived from the experimental results and calculations: the dye molecule sits close to the channel walls with the carbonyl group pointing to an Al3+ site of the zeolite framework. A secondary interaction was observed between the fluorenone's aromatic ring and the zeolite's charge-compensating cations. [source] Structure of Pyridazine in the S1 State: Experiment and TheoryCHEMPHYSCHEM, Issue 11 2008Doo-Sik Ahn Abstract The molecular structure of pyridazine in the first electronically excited state (S1) is deduced from the combined use of resonance-enhanced two-photon ionization and mass-analyzed threshold ionization spectroscopic methods. The equation-of-motion coupled-cluster single and double (EOM,CCSD) calculation gives the distorted planar geometry for the most stable structure of the S1 pyridazine. The symmetry constraint of C2v is relaxed to that of Cs, and consequently many in-plane vibrational modes are found to be optically active in both S1,S0 and D0,S1 excitation spectra, being appropriately assigned from the comparison of their frequencies with ab initio values. This indicates that the S1,S0 excitation is partially localized, and provides an alternative explanation for the long-standing spectroscopic puzzle in S1 pyridazine. [source] Electronic Spectra of Ti(IV) in Zeolites: An Ab Initio ApproachCHEMPHYSCHEM, Issue 7 2005Ettore Fois Prof. Dr. Charge transfer in Ti,zeolites: Model titanium,zeolites containing a single Ti(IV) tetrahedral species were built and their electronic excitation spectra were calculated (see picture) via time-dependent density functional theory (TDDFT). A multiple-band profile was obtained in each case, thus highlighting that the features observed in the UV/Vis spectra are not a direct evidence of chemically different Ti(IV) sites. [source] Minocycline-Based Europium(III) Chelate Complexes: Synthesis, Luminescent Properties, and Labeling to StreptavidinHELVETICA CHIMICA ACTA, Issue 11 2009Takuya Nishioka Abstract Two chelate ligands for europium(III) having minocycline (=(4S,4aS,5aR,12aS)-4,7-bis(dimethylamino)-1,4,4a,5,5a,6,11,12a-octahydro-3,10,12,12a-tetrahydroxy-1,11-dioxonaphthacene-2-carboxamide; 5) as a VIS-light-absorbing group were synthesized as possible VIS-light-excitable stable Eu3+ complexes for protein labeling. The 9-amino derivative 7 of minocycline was treated with H6TTHA (=triethylenetetraminehexaacetic acid=3,6,9,12-tetrakis(carboxymethyl)-3,6,9,12-tetraazatetradecanedioic acid) or H5DTPA (=diethylenetriaminepentaacetic acid=N,N -bis{2-[bis(carboxymethyl)amino]ethyl}glycine) to link the polycarboxylic acids to minocycline. One of the Eu3+ chelates, [Eu3+(minocycline-TTHA)] (13), is moderately luminescent in H2O by excitation at 395,nm, whereas [Eu3+(minocycline-DTPA)] (9) was not luminescent by excitation at the same wavelength. The luminescence and the excitation spectra of [Eu3+(minocycline-TTHA)] (13) showed that, different from other luminescent EuIII chelate complexes, the emission at 615,nm is caused via direct excitation of the Eu3+ ion, and the chelate ligand is not involved in the excitation of Eu3+. However, the ligand seems to act for the prevention of quenching of the Eu3+ emission by H2O. The fact that the excitation spectrum of [Eu3+(minocycline-TTHA)] is almost identical with the absorption spectrum of Eu3+ aqua ion supports such an excitation mechanism. The high stability of the complexes of [Eu3+(minocycline-DTPA)] (9) and [Eu3+(minocycline-TTHA)] (13) was confirmed by UV-absorption semi-quantitative titrations of H4(minocycline-DTPA) (8) and H5(minocycline-TTHA) (12) with Eu3+. The titrations suggested also that an 1,:,1 ligand Eu3+ complex is formed from 12, whereas an 1,:,2 complex was formed from 8 minocycline-DTPA. The H5(minocycline-TTHA) (12) was successfully conjugated to streptavidin (SA) (Scheme,5), and thus the applicability of the corresponding Eu3+ complex to label a protein was established. [source] Photodynamic therapy with violet light and topical ,-aminolaevulinic acid in the treatment of actinic keratosis, Bowen's disease and basal cell carcinomaJOURNAL OF THE EUROPEAN ACADEMY OF DERMATOLOGY & VENEREOLOGY, Issue 6 2001AT Dijkstra Abstract Background Most clinical studies using photodynamic therapy (PDT) with topical application of ,-aminolaevulinic acid (,-ALA) use red light because it allows greater depth of penetration. However, given the porphyrin-like spectrum of ,-ALA-induced photosensitivity, violet light provides a maximal overlap with the excitation spectrum of protoporphyrin IX, meaning that PDT with violet light uses less light energy to induce the phototoxic reaction. Aim To study the efficacy of violet light in combination with topical ,-ALA PDT in the treatment of premalignant and malignant skin lesions. Methods Eight hours after 20%,-ALA was applied topically, photoirradiation was performed with an incoherent light source (Philips HPM-10, 400 W) emitting predominantly violet light (400,450 nm). Lesions received 10,20 J/cm2 during an exposure time of 30 min. The 38 subjects treated included three with basal cell naevus syndrome with multiple (> 30) superficial and nodular basal cell carcinomas (BCCs), one subject had multiple lesions of Bowen's disease, involving 50% of the scalp, and the remaining 34 subjects presented a total of 35 superficial BCCs, 10 nodular BCCs, four large solar keratoses and five solitary lesions of Bowen's disease. Results Complete remission both clinically and histologically was seen after a single treatment in 82% of the superficial BCCs (100% after a second treatment), 50% of the nodular BCCs, one of the four solar keratosis lesions (partial remission in the other three) and 90,100% of the solitary lesions of Bowen's disease. Conclusions ,-ALA PDT using violet light appears to be a well tolerated and effective alternative treatment for premalignant and malignant skin lesions, especially when there are multiple lesions or large patches comprising a large area of skin. [source] Spectroscopic studies on origination of the peak at 730 nm in delayed fluorescence of chloroplastsLUMINESCENCE: THE JOURNAL OF BIOLOGICAL AND CHEMICAL LUMINESCENCE, Issue 4 2007Lizhang Zeng Abstract The origination of the peak at 730 nm in the delayed fluorescence (DF) spectrum of chloroplasts was studied using various optical analysis methods. The DF spectrum showed that the main emission peak was at about 685 nm, with a small shoulder at 730 nm when the chloroplast concentration was < 7.8 µg/mL. The intensity of the peak at 685 nm decreased, while the intensity of the peak at 730 nm increased, when the chloroplast concentrations were increased from 7.8 to 31.2 µg/mL. With the concentration increasing, the peak at 730 nm became dominant while the peak at 685 nm finally disappeared. The DF decay kinetic curves showed that the intensity of the peak at 730 nm decayed as the same speed as the intensity of the peak at 685 nm during the entire relaxation process (0.5,30.5 s). With the excitation wavelength at 685 nm, the emission intensity was stronger in the excitation spectrum at 730 nm. The absorption spectrum demonstrated that the ratio A685:A730 remained almost constant when the chloroplast concentration increased. The results suggest that the peak at 730 nm appearing in DF is mainly contributed by the fluorescence of photosystem I (PSI), generated by the re-absorption of 685 nm band DF. Copyright © 2007 John Wiley & Sons, Ltd. [source] | |||||||||||||||||||