951 research outputs found

    Comment on 'Energy transfer and upconversions in cubic Cs2NaYCl6:Er+3 and Cs2NaErCl6'

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    Well-resolved luminescence from the crystal-field level 2H(2)9/2 aΓ8 at 36236 cm-1 to 34 lower levels has been observed for Cs2NaErCl6 upon pulsed laser excitation at 273.9 nm. The assignments enable the location and identification of the upconversion luminescence state in the study of Hasan et al. [Phys. Rev. B 56, 4518 (1997)] and support a two-photon vibronic excitation mechanism in the latter case. The experimentally determined energy for the 2H(2)9/2 aΓ8 state differs considerably from the calculated value. The temporal behavior of blue upconverted luminescence from the 2G9/2 state is reproduced from an analytical expression, and it is shown that the alternative fitting procedure does not enable the two-ion upconversion rate W to be well determined.published_or_final_versio

    A stoichiometric terbium-europium dyad molecular thermometer: energy transfer properties

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    © 2018, The Author(s). The optical thermometer has shown great promise for use in the fields of aeronautical engineering, environmental monitoring and medical diagnosis. Self-referencing lanthanide thermo-probes distinguish themselves because of their accuracy, calibration, photostability, and temporal dimension of signal. However, the use of conventional lanthanide-doped materials is limited by their poor reproducibility, random distance between energy transfer pairs and interference by energy migration, thereby restricting their utility. Herein, a strategy for synthesizing hetero-dinuclear complexes that comprise chemically similar lanthanides is introduced in which a pair of thermosensitive dinuclear complexes, cycTb-phEu and cycEu-phTb, were synthesized. Their structures were geometrically optimized with an internuclear distance of approximately 10.6Å. The sensitive linear temperature-dependent luminescent intensity ratios of europium and terbium emission over a wide temperature range (50–298K and 10–200K, respectively) and their temporal dimension responses indicate that both dinuclear complexes can act as excellent self-referencing thermometers. The energy transfer from Tb3+ to Eu3+ is thermally activated, with the most important pathway involving the 7F1 Eu3+J-multiplet at room temperature. The energy transfer from the antenna to Eu3+ was simulated, and it was found that the most important ligand contributions to the rate come from transfers to the Eu3+ upper states rather than direct ligand–metal transfer to 5D1 or 5D0. As the first molecular-based thermometer with clear validation of the metal ratio and a fixed distance between the metal pairs, these dinuclear complexes can be used as new materials for temperature sensing and can provide a new platform for understanding the energy transfer between lanthanide ions

    Ultraviolet f→f emission and crystal field analysis for Er3+ in Cs2NaErCl6

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    Luminescence is reported from the 2I11/2 level of Er3+, in the cubic elpasolite lattices Cs2NaErCl6 and Cs2NaYCl6. Altogether, with the use of ultraviolet laser excitation, 11 transitions from 2I11/2 Γ7 (at 40 668 cm-1) to lower term multiplets have been observed and assigned. Transitions are also reported from the 2K13/2 Γ6 level at 32 613 cm-1. The absence of emission from 2P3/2 (at 31 367 cm-1) under the experimental conditions is rationalized. Up-conversion to 2H(2)9/2, which is not due to two-photon absorption, is reported for Cs2NaErCl6 under blue pulsed laser excitation. Trap emission from 2G9/2 defect sites has been observed under ultraviolet excitation. A preliminary investigation has been made of the electronic absorption spectra of Cs2NaErCl6 and 58 Kramers quartet and doublet levels have been assigned, with a further 18 levels uncertain. The energy-level fit to 58 levels with total degeneracy 180 has been performed with a mean deviation of 20.4 cm-1, which is improved to 16.8 cm-1 if an empirical correction to the diagonal reduced matrix element of U4 for the 2H(2) term is included. The average error is similar for the 18 uncertain levels (total degeneracy 52). A comparison is included with the energy-level parametrizations of other Er3+ systems.published_or_final_versio

    Photocatalytic degradation of methylparathion - An endocrine disruptor by Bi??-doped TiO?

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    Author name used in this publication: X. Z. LiAuthor name used in this publication: G. K. H. PangAuthor name used in this publication: P. A. Tanner2005-2006 > Academic research: refereed > Publication in refereed journalAccepted ManuscriptPublishe

    4f-5d transitions of Pr3+ in elpasolite lattices

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    The 4f5d→4f2 emission spectra of Cs2MPrCl6 (M = Na,Li) and CS2NaYCl6:Pr3+ have been recorded at temperatures down to 10 K. The spectra of Pr3+ in the cubic host Cs2NaYCl6 are the most clearly resolved, and 15 transitions to terminal crystal field levels of symmetry representations Γ5g and Γ4g have been observed and assigned, thereby inferring that the symmetry representation of the lowest 4f5d crystal field level is Γ3u. Each transition is characterized by strong progressions in two totally symmetric vibrational modes. The relative displacement of the potential energy curves for the 4f2 and 4f5d crystal field levels, along the α1g internal mode coordinate, is small, being only about 5 pm. The 10-K ultraviolet absorption spectra of CS2NaYCl6:Pr3+ are assigned to transitions from the [3H4] Γ1g electronic ground state to terminal Γ4u crystal field levels of 4f5d. Nontotally symmetric gerade vibrational modes only provide minor intensity contributions. The large energy gap between the d-f emission and f-d absorption spectra of Pr3+ in the cubic elpasolite host is rationalized. The 8-K excitation spectra of Cs2NaPrCl6 and Cs2NaYCl6:Pr3+, excited by synchrotron radiation, show that the transitions to 4f5d fall into two groups. The energy levels and wave vectors of the (independent) 4f2 and 4f5d configurations of Pr3+ have been calculated using a model which includes spin-orbit coupling and crystal field and Coulomb interactions, as well as the configuration interaction of 4f2 with 4f6p. Using the eigenvector of the predominantly high-spin, lowest excited crystal field level of 4f5d, the emission intensities are reasonably well simulated. However, the refinement of the 4f2→4f5d absorption intensities requires a more detailed knowledge of the crystal field energy level scheme of 4f5d. The configuration interaction of 4f5d with 4f6s and 4f5g is discussed.published_or_final_versio

    Upconversion luminescence of an insulator involving a band to band multiphoton excitation process

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    Author name used in this publication: Jian Hua Hao2010-2011 > Academic research: refereed > Publication in refereed journalVersion of RecordPublishe

    The Changing Epidemiology of Malaria in Ifakara Town, Southern Tanzania.

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    Between 1995 and 2000 there were marked changes in the epidemiology of malaria in Ifakara, southern Tanzania. We documented these changes using parasitological and clinical data from a series of community- and hospital-based studies involving children up to the age of 5 years. There was a right shift and lowering in the age-specific parasite prevalence in the community-based cohort studies. The incidence of clinical malaria in placebo-receiving infants in additional study cohorts dropped from 0.8 in 1995 to 0.43 episodes per infant per year in 2000, an incidence rate ratio of 0.53 (95% confidence interval: 0.404, 0.70, P<0.0001). At the same time, there was an increase in the total number of malaria admissions and a marked right shift in the age pattern of these admissions (median age in 1995 1.55 years vs. 2.33 in 2000, P<0.0001). However, the burden of malaria deaths remained in infants. We discuss how these dramatic changes in the epidemiology of malaria may have arisen from the use of currently available malaria control tools. Caution is required in the interpretation of hospital-based data as it is likely to underestimate the impact of anaemia on mortality in the community, where most paediatric deaths occur. Even in low/moderate malaria transmission settings, where older children suffer most malaria episodes, targeting effective malaria control at infants may produce important reductions in infant mortality caused by malaria

    A multi-compartment single and multiple dose pharmacokinetic comparison of rectally applied tenofovir 1% gel and oral tenofovir disoproxil fumarate

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    This Phase 1, randomized, two-site (United States), double-blind, placebo-controlled study enrolled 18 sexually abstinent men and women. All received a single 300-mg dose of oral tenofovir disoproxil fumarate (TDF) and were then randomized 2:1 to receive single and then seven daily rectal exposures of vaginally-formulated tenofovir (TFV) 1% gel or a hydroxyethyl cellulose (HEC) placebo gel. Blood, colonic biopsies and rectal and vaginal mucosal fluids were collected after the single oral TDF, the single topical TFV gel dose, and after 7 days of topical TFV gel dosing for extracellular analysis of TFV and intracellular analysis of the active metabolite tenofovir diphosphate (TFVdp) in peripheral blood mononuclear cells (PBMCs) and isolated mucosal mononuclear cells (MMC), including CD4+ and CD4- cell subsets. With a single rectal dose, TFV plasma concentrations were 24-33 fold lower and half-life was 5 h shorter compared to a single oral dose (p = 0.02). TFVdp concentrations were also undetectable in PBMCs with rectal dosing. Rectal tissue exposure to both TFV and TFVdp was 2 to 4-log10 higher after a single rectal dose compared to a single oral dose, and after 7 daily doses, TFVdp accumulated 4.5 fold in tissue. TFVdp in rectal tissue homogenate was predictive (residual standard error, RSE = 0.47) of tissue MMC intracellular TFVdp concentration, with the CD4+ cells having a 2-fold higher TFVdp concentration than CD4- cells. TFV concentrations from rectal sponges was a modest surrogate indicator for both rectal tissue TFV and TFVdp (RSE = 0.67, 0.66, respectively) and plasma TFV (RSE = 0.38). TFV penetrates into the vaginal cavity after oral and rectal dosing, with rectal dosing leading to higher vaginal TFV concentrations (p<0.01)

    Arbuscular mycorrhizal fungal community composition is altered by long-term litter removal but not litter addition in a lowland tropical forest

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    Tropical forest productivity is sustained by the cycling of nutrients through decomposing organic matter. Arbuscular mycorrhizal (AM) fungi play a key role in the nutrition of tropical trees, yet there has been little experimental investigation into the role of AM fungi in nutrient cycling via decomposing organic material in tropical forests. We evaluated the responses of AM fungi in a long-term leaf litter addition and removal experiment in a tropical forest in Panama. We described AM fungal communities using 454-pyrosequencing, quantified the proportion of root length colonised by AM fungi using microscopy, and estimated AM fungal biomass using a lipid biomarker. AM fungal community composition was altered by litter removal but not litter addition. Root colonisation was substantially greater in the superficial organic layer compared with the mineral soil. Overall colonisation was lower in the litter removal treatment, which lacked an organic layer. There was no effect of litter manipulation on the concentration of the AM fungal lipid biomarker in the mineral soil. We hypothesise that reductions in organic matter brought about by litter removal may lead to AM fungi obtaining nutrients from recalcitrant organic or mineral sources in the soil, besides increasing fungal competition for progressively limited resources.Smithsonian Tropical Research Institute; Cambridge Home and European Scholarship; Department of Plant Sciences, Cambridge; Cambridge Philosophical Society; European Research Council; European Union's Seventh Framework Programme. Grant Number: FP/2007-201
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