Formation of thin luminescent Eu3+-LB films by in situ coordination with 2,3,5,6-tetra(2 '-pyridyl)pyrazine and 1-octadecanol in pure and mixed Langmuir monolayers

The in situ complexation between 2,3,5,6-tetra(2-pyridyl)pyrazine (tppz) molecules and europium ions at the air-liquid interface by means of mixed 1-octadecanol Langmuir films is reported. These films were transferred to solid supports by means of the Langmuir-Blodgett (LB) technique. The EDS maps attested the homogeneity of the LB films as well as the presence of the europium ions. The mixed alcohol/tppz LB film contained a larger amount of europium ions as compared to the pure octadecanol LB film. This work reports the production of a thin luminescent Eu3+ film containing europium ions using only alcohol molecules as ligands an unexpected result, since it is well known that there is an occurrence of non-radiative deactivation of excited europium by hydroxyl groups. Europium ion multiple binding sites were detected from lifetime decay measurements of these films in the presence of tppz molecules. (C) 2012 Elsevier B.V. All rights reserved.

Temperature performance of AlGaN/GaN MOS-HEMTs on Si substrates using Gd2O3 as gate dielectric

GaN based high electron mobility transistors have draw great attention due to its potential in high temperature, high power and high frequency applications [1, 2]. However, significant gate leakage current is still one of the issues which need to be solved to improve the performance and reliability of the devices [3]. Several research groups have contributed to solve this problem by using metal���oxide���semiconductor HEMTs (MOSHEMTs), with a thin dielectric layer, such as SiO2 [4], Al2O3 [5], HfO2 [6] and Gd2O3 [7] between the gate and the barrier layer on AlGaN/GaN heterostructures. Gd2O3 has shown low interfacial density of states(Dit) with GaN and a high dielectric constant and low electrical leakage currents [8], thus is considered as a promising candidate for the gate dielectrics on GaN. MOS-HEMTs using Gd2O3 grown by electron-beam heating [7] or molecular beam epitaxy (MBE) [8] on GaN or AlGan/GaN structure have been investigated, but further research is still needed in Gd2O3 based AlGaN/GaN MOSHEMTs.

Diplomatic Spin: EU3+3 talks on Iran���s nuclear file. CEPS Commentary, 21 November 2014

The Joint Plan of Action agreed upon with Iran on 24 November 2013 gave negotiators one year to forge a comprehensive agreement that restricts the country���s ability to militarise its nuclear programme. That deadline will lapse in the next few days and diplomats involved in the talks have been trying to rein in expectations that a deal will be struck on time. Satisfying domestic constituencies in Iran and the US is what makes the politics of dealing with the nuclear file so much harder than the physics of slowing down the nuclear programme. Any future deal will have to stand on its own merits, enabling Iran and the EU3+3 to cooperate on the other geopolitical challenges they face. Both parties should therefore balance their demands with what they can realistically offer and make concessions to reach a compromise. The author of this CEPS Commentary argues that if no deal is reached on November 24th, then diplomacy should be allowed to keep on spinning for a few more months.

Thermal stability study of AlGaN/GaN MOS-HEMTs using Gd2O3 as gate dielectric

Thermal stability of AlGaN/GaN MOS-HEMTs and -diodes using Gd_(2)O_(3) are investigated by means of different thermal cycles and storage tests up to 500��C for one week. IV DC and pulsed characteristics of the devices before and after the processes are evaluated and compared with conventional HEMTs. Results show that the devices with Gd_(2)O_(3) dielectric layer have lower leakage current and a more stable behavior during thermal treatment processes compared with conventional devices. In fact, an excellent on/off ratio of about 108 and a stable V_(t) is observed after storage at high temperature. The beneficial effects of Gd_(2)O_(3) on trapping effects of MOS-HEMTs are also dis-cussed.

Radiative Behaviour of Gd2O3:Er/Yb nanoparticles under near infrared illumination

Upconverting nanoparticles have attracted much attention in science recently, speci���cally in view of medical and biological applications such as live imaging of cell temperatures or cancer treatment. The previously studied system of gadolinium oxide nanorods co-doped with erbium and ytterbium and decorated with di���erent number densities of gold nanoparticles has been studied. So far, these particles have been proven as e���cient nanothermometers in a temperature range from 300 up to 2000 K. In this work, a more detailed study on the morphological and radiative behaviour of these particles has been conducted. It was found that the laser power threshold for the onset of the black body radiation decreases strongly with the increase in the gold concentration. The temperature of the onset itself seems to remain approximately constant. The heating e���ciency was determined to increase signi���cantly with the gold concentration. The morphological study revealed that the temperature at the black body radiation threshold was not enough to induce any signi���cant transformation in neither the nanorods nor the gold nanoparticles, as was expected from comparison with literature. However, signi���cant changes in radiative properties and the morphology were detected for powders that underwent strong laser heating until the emission of brightly visible black body radiation.

Poli-l��quidos i��nicos e complexos sol��veis de Eu3+ e Tb3+ : bioimageamento celular seletivo

Disserta����o (mestrado)���Universidade de Bras��lia, Instituto de Qu��mica, Programa de P��s-Gradua����o em Qu��mica, 2015.

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.

S��ntese, aplica����o e avalia����o da toxicidade aguda de complexo org��nico �� base de eur��pio proposto como marcador fotoluminescente para a Identifica����o de res��duos de tiro

Um complexo de alta fotoluminesc��ncia �� proposto como marcador ��ptico para a identifica����o de res��duos de tiro (GSR). O marcador �� o complexo [Eu(PIC)3(NMK)3], de f��rmula molecular Eu(C6H2N3O7)3.(C7H13NO)3, que apresenta o ��on Eu3+ e os ligantes ��cido p��crico (PIC) e n-metil-��-caprolactama (NMK). Foi realizada a caracteriza����o quimicamente atrav��s de espectroscopia de emiss��o, espectroscopia de infravermelho com transformada de Fourier (FTIR), termogravimetria e an��lise t��rmica diferencial (TG/DTA), e espectrometria de massas com ioniza����o por eletrospray e resson��ncia ciclotr��nica de ��ons por transformada de Fourier (ESI-FT-ICR MS), e, em seguida, foram adicionadas diferentes massas do complexo a muni����es convencionais (de 2 a 50 mg por cartucho). Ap��s os tiros, o GSR marcado foi visualmente e quimicamente detectado por irradia����o UV (�� = 395 nm) e ESI-FT-ICR MS, respectivamente. Os resultados mostraram uma fotoluminesc��ncia eficiente e duradoura, sendo facilmente vis��vel sobre a superf��cie do alvo, no ambiente, no cartucho deflagrado, na arma de fogo, e sobre as m��os e bra��os do atirador quando utilizada massa a partir de 25 mg do marcador em cartuchos .38 e 50 mg em cartuchos .40. Sua toxicidade aguda tamb��m foi avaliada empregando-se o Protocolo 423 da Organiza����o para a Coopera����o e Desenvolvimento Econ��mico (OECD) e apresentou DL50 de 1000 mg.kg-1, sendo classificado como de categoria 4 na escala do Sistema Globalmente Harmonizado de Classifica����o e Rotulagem de Produtos Qu��micos (GHS), considerado, portanto, de m��dia toxicidade. O composto mostrou ser menos t��xico do que os componentes inorg��nicos de muni����es convencionais (em especial o Pb), justificando o seu emprego como marcador de GSR.

Eco-friendly luminescent hybrid materials based on EuIII and LiI co-doped chitosan

Biopolymer-based materials have been of particular interest as alternatives do synthetic polymers due to their low toxicity, biodegradability and biocompatibility. Among them, chitosan is one of the most studied ones and has recently been investigated for the application as solid state polymer electrolytes. Furthermore, it can serve as a host for luminescent species such as rare earth ions, giving rise to materials with increased functionality, of particular interest for electrochemical devices. In this study, we investigate chitosan based luminescent materials doped wit Eu3+ and Li+ triflate salts from the structural, photophysical and conductivity points of view. Because the host presents a broad emission band in the blue to green, while Eu3+ emits in the red, fine tuning of emission colour and/or generation of white light is possible by optimizing composition and excitation scheme. Europium lifetimes (5D0) are in the range 270 ��� 350 ��s and quantum yields are as high as 2%. Although Li+ does not interfere with the luminescent properties, it grants ion-conducting properties to the material suggesting that a combination of both properties could be further explored in multifunctional device.

An evaluation of the inorganic and organic geochemistry of the San Vicente Mississippi Valley-type zinc-lead district, central Peru: Implications for ore fluid composition, mixing processes, and sulfate reduction

Mississippi Tialley-type zinc-lead deposits and ore occurrences in the San Vicente belt are hosted in dolostones of the eastern Upper Triassic to Lower Jurassic Pucara basin, central Peru. Combined inorganic and organic geochemical data from 22 sites, including the main San Vicente deposit, minor ore occurrences, and barren localities, provide better understanding of fluid pathways and composition, ore precipitation mechanisms, Eh-pH changes during mineralization, and relationships between organic matter and ore formation. Ore-stage dark replacement dolomite and white sparry dolomite are Fe and rare earth element (REE) depleted, and Mn enriched, compared to the host dolomite. In the main deposit, they display significant negative Ce and probably Eu anomalies. Mixing of an incoming hot, slightly oxidizing, acidic brine (H2CO3 being the dominant dissolved carbon species), probably poor in REE and Fe, with local intraformational, alkaline, reducing waters explains the overall carbon and oxygen isotope variation and the distributions of REE and other trace elements in the different hydrothermal carbonate generations. The incoming ore fluid flowed through major aquifers, probably basal basin detrital units, with limited interaction with the carbonate host rocks. The hydrothermal carbonates show a strong regional chemical homogeneity, indicating access of the ore fluids by interconnected channelways near the ore occurrences. Negative Ce anomalies in the main deposit, that are absent at the district scale, indicate local ore-fluid chemical differences. Oxidation of both migrated and indigenous hydrocarbons by the incoming fluid provided the local reducing conditions necessary for sulfate reduction to H2S, pyrobitumen precipitation, and reduction of Eu3+ to Eu2+. Fe-Mn covariations, combined with the REE contents of the hydrothermal carbonates, are consistent with the mineralizing system shifting from reducing/rock-dominated to oxidizing/fluid-dominated conditions following ore deposition. Sulfate and sulfide sulfur isotopes support sulfide origin from evaporite-derived sulfate by thermochemical organic reduction; further evidence includes the presence of C-13-depleted calcite cements (similar to-12 parts per thousand delta(13)C) as sulfate pseudomorphs, elemental sulfur, altered organic matter in the host dolomite, and isotopically heavier, late, solid bitumen. Significant alteration of the indigenous and extrinsic hydrocarbons, with absent bacterial membrane biomarkers (hopanes) is observed. The light delta(34)S of sulfides from small mines and occurrences compared to the main deposit reflect a local contribution of isotopically light sulfur, evidence of local differences in the ore-fluid chemistry.

Troca i��nica no estado s��lido de eur��pio3+ em ze��lita Y: influ��ncia do tempo de rea����o

Rare earth elements supported in zeolites are the most important catalysts in the fluid cracking of petroleum. The solid state ion exchange of Eu3+ in Y zeolite was investigated. First of all, the hydrated EuCl3 was well mixed in a ball mill and was then heated at 300��C for different times. The quantitative determination of Eu3+ showed that the degree of ion exchange depends on the reaction time at constant temperature, being ~95% in 4 h. The X-ray study showed that the crystallinity of the zeolite is little affected by the exchange procedure. The study of spectroscopic properties of Eu3+, emission spectra and lifetime, give information about the migration and position of the ion in the zeolite cages.

Coordena����o local do Eu(III) em h��bridos org��nicos/inorg��nicos emissores de luz branca

Eu3+ luminescence and EXAFS (Extended X-ray Absorption Fine Structure) results are presented for organic-inorganic hybrid gel hosts composed of a siliceous network to which small chains of oxyethylene units are covalently grafted by means of urea bridges. Coordination numbers for Eu3+ ions range from 12.8 to 9.7 with increasing Eu3+ concentration while the Eu3+-first neighbours mean distance is found to be constant at 2.48-2.49 �� in the same concentration range. Emission spectra display a broad band in the green/blue spectral region superposed to narrow lines appearing in the yellow/red region in such a way that for the eyes emission appears white. The broad band is assigned to intrinsic NH groups emission and also to electron-hole recombination in the nanosised siliceous domains. The narrow lines are assigned to intra-4f6, 5D0->7F0-4 Eu3+ transitions and from the energy position of the 7F0-4 levels a mean distance could be calculated for the Eu3+-first neighbours. The calculated results are in good agreement with the experimental ones obtained from EXAFS analysis.

Design and production of protein nanostructures for biomolecular detection

Particulate nanostructures are increasingly used for analytical purposes. Such particles are often generated by chemical synthesis from non-renewable raw materials. Generation of uniform nanoscale particles is challenging and particle surfaces must be modified to make the particles biocompatible and water-soluble. Usually nanoparticles are functionalized with binding molecules (<i>e.g.</i>, antibodies or their fragments) and a label substance (if needed). Overall, producing nanoparticles for use in bioaffinity assays is a multistep process requiring several manufacturing and purification steps. This study describes a biological method of generating functionalized protein-based nanoparticles with specific binding activity on the particle surface and label activity inside the particles. Traditional chemical bioconjugation of the particle and specific binding molecules is replaced with genetic fusion of the binding molecule gene and particle backbone gene. The entity of the particle shell and binding moieties are synthesized from generic raw materials by bacteria, and fermentation is combined with a simple purification method based on inclusion bodies. The label activity is introduced during the purification. The process results in particles that are ready-to-use as reagents in bioaffinity. Apoferritin was used as particle body and the system was demonstrated using three different binding moieties: a small protein, a peptide and a single chain Fv antibody fragment that represents a complex protein including disulfide bridge.If needed, Eu3+ was used as label substance. The results showed that production system resulted in pure protein preparations, and the particles were of homogeneous size when visualized with transmission electron microscopy. Passively introduced label was stably associated with the particles, and binding molecules genetically fused to the particle specifically bound target molecules. Functionality of the particles in bioaffinity assays were successfully demonstrated with two types of assays; as labels and in particle-enhanced agglutination assay. This biological production procedure features many advantages that make the process especially suited for applications that have frequent and recurring requirements for homogeneous functional particles. The production process of ready, functional and watersoluble particles follows principles of ���green chemistry���, is upscalable, fast and cost-effective.

Filmes de tit��nio-sil��cio preparados por "spin" e "dip-coating"

The conditions for the preparation of luminescent materials, consisting of Eu3+ ions entrapped in a titanium matrix, in the forma of a thin film, using the sol-gel process, are described. The films were obtained from sols prepared with TEOS and TEOT, in the presence of acetylacetone as the hidrolysis-retarding agent, using the dip-coating and spin-coating techniques. The influence of these techniques on the films based on titanium and silicon are presented. The Eu3+ was used as a luminescent probe. The films have been characterized by luminescence, reflection and transmittance. The thickness of the films could be related to the preparation procedure. Transparent thin films have been prepared by dip-coating technique.