Persistent luminescence mechanisms: human imagination at work

The present status and future progress of the mechanisms of persistent luminescence are critically treated with the present knowledge. The advantages to be achieved by a further need as well as the pitfalls of the excessive use of imagination are shown. As usual, in the beginning of the present era of persistent luminescence since the mid 1990s, the imagination played a more important role than the sparse solid experimental data and the chemical common sense and knowledge was largely ignored. Since some five years, the mechanistic studies seem to have reached the maturity and - perhaps deceivingly - it seems that there are only details to be solved. However, the development of red emitting nanocrystalline materials poses a challenge also to the more fundamental studies and interpretation. The questions still luring in the darkness include the problems how the increased surface area affects the defect structure and how the "persistent energy transfer" really works. There is still some light to be thrown onto these matters starting with agreeing on the terminology: the term phosphorescence should be abandoned altogether. The long lifetime of persistent luminescence is due to trapping of excitation energy, not to the forbidden nature of the luminescent transition. However, the technically well-suited term "afterglow" should be retained for harmful, short persistent luminescence. (C) 2012 Optical Society of America

Film based on Y2O3: Eu3+ (5 mol% of Eu3+) for flat panel display

This paper reports on Y2O3:Eu3+ containing 1 mol% of Ag-0 nanoparticle films recovered with a SiO2 layer by using glass foil as a substrate for a possible optical display device application. The obtained film showed an intense emission at 612 nm due to the Eu3+ 5D0 -> F-7(2) hypersensitive transition, a high transmittance in that emission range, an excellent optical quality, and a high absorption only below 300 nm. Moreover, despite the presence of the SiO2 layer used to improve the phosphor adhesion on Corning (R) foil substrates, the intensity ratios between the emissions assigned to Eu3+ D-5(0) -> F-7(2) (dipole electric transition) and D-5(0) -> F-7(1) (dipole magnetic transition) were not affected by it. The x and y coordinate values found in the 1931 Commission Internationale de l'Eclairage Chromaticity Diagram for this film reveal that it has a suitable pure red color emission for optical displays devices. (C) 2012 Elsevier B. V. All rights reserved.

A systematic study of transfection efficiency and cytotoxicity in HeLa cells using iron oxide nanoparticles prepared with organic and inorganic bases

Magnetic iron oxide nanoparticles (magnetite) (MNPs) were prepared using different organic and inorganic bases. Strong inorganic base (KOH) and organic bases (NH4OH and 1,4-diazabicyclo[2.2.2]octane (DABCO)) were used in the syntheses of the MNPs. The MNPs were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM). Fourier transform infrared spectroscopy (FT-IR) and magnetization measurements. MNPs prepared with strong inorganic base yielded an average size of 100 nm, whereas the average size of the MNPs prepared with the organic bases was 150 nm. The main competitive phase for MNPs prepared with the strong inorganic and organic bases was maghemite; however, syntheses with KOH yielded a pure magnetite phase. The transfection study performed with the MNPs revealed that the highest transfection rate was obtained with the MNPs prepared with KOH (74%). The correlation between the magnetic parameters and the transfection ratio without transfection agents indicated that MNPs prepared with KOH were a better vector for possible applications of these MNPs in biomedicine. HeLa cells incubated with MNP-KOH at 10 mu g/mL for 24 and 48 h exhibited a decrease in population in comparison with the control cells and it was presumably related to the toxicity of the MNPs. However, the cells incubated with MNP-KOH at 50 and 100 mu g/mL presented a very small difference in the viability between the cell populations studied at 24 and 48 h. These data illustrate the viability of HeLa cells treated with MNP-KOH and suggest the potential use of these MNPs in biomedical applications. (C) 2012 Elsevier B.V. All rights reserved.

Characterization of an extrapolation chamber for low-energy X-rays: Experimental and Monte Carlo preliminary results

The extrapolation chamber is a parallel-plate ionization chamber that allows variation of its air-cavity volume. In this work, an experimental study and MCNP-4C Monte Carlo code simulations of an ionization chamber designed and constructed at the Calibration Laboratory at IFEN to be used as a secondary dosimetry standard for low-energy X-rays are reported. The results obtained were within the international recommendations, and the simulations showed that the components of the extrapolation chamber may influence its response up to 11.0%. (C) 2011 Elsevier Ltd. All rights reserved.

Astrobiology in Brazil: early history and perspectives

This review reports the Brazilian history in astrobiology, as well as the first delineation of a vision of the future development of the field in the country, exploring its abundant biodiversity, highly capable human resources and state-of-the-art facilities, reflecting the last few years of stable governmental investments in science, technology and education, all conditions providing good perspectives on continued and steadily growing funding for astrobiology-related research. Brazil is growing steadily and fast in terms of its worldwide economic power, an effect being reflected in different areas of the Brazilian society, including industry, technology, education, social care and scientific production. In the field of astrobiology, the country has had some important landmarks, more intensely after the First Brazilian Workshop on Astrobiology in 2006. The history of astrobiology in Brazil, however, is not so recent and had its first occurrence in 1958. Since then, researchers carried out many individual initiatives across the country in astrobiology-related fields, resulting in an ever growing and expressive scientific production. The number of publications, including articles and theses, has particularly increased in the last decade, but still counting with the effort of researchers working individually. That scenario started to change in 2009, when a formal group of Brazilian researchers working with astrobiology was organized, aiming at congregating the scientific community interested in the subject and to promote the necessary interactions to achieve a multidisciplinary work, receiving facilities and funding from the University de Sao Paulo and other funding agencies. Received 29 February 2012, accepted 17 May 2012, first published online 18 July 2012

Terbium(III) and dysprosium(III) 8-connected 3D networks containing 2,5-thiophenedicarboxylate anion: Crystal structures and photoluminescence studies

Two novel coordination polymers with the formula {[Ln(2)(2,5-tdc)(3)(dmso)(2)].H2O}(n) (Ln = Tb(III) for (1) and Dy(III) for (2)), (2,5-tdc(2-) = 2,5-thiophenedicarboxylate and dmso = dimethylsulfoxide) have been synthesized by the diffusion method and characterized by thermal analysis, vibrational spectroscopy and single crystal X-ray diffraction analysis. Structure analysis reveals that 2,5-tdc(2-) play a versatile role toward different lanthanide ions to form three-dimensional metal-organic frameworks (MOFs) in which the lanthanides ions are heptacoordinated. Photophysical properties were studied using excitation and emission spectra, where the photoluminescence data show the high emission intensity of the characteristic transitions D-5(4 ->) F-7(J) (J= 6, 5, 4 and 3) for (1) and (F9/2 -> HJ)-F-4-H-6 (J = 15/2, 13/2 and 11/2) for (2), indicating that 2,5-tdc(2-) is a good sensitizer. (C) 2012 Elsevier Ltd. All rights reserved.

An evaluation of dosimetric characteristics of MAGIC gel modified by adding formaldehyde (MAGIC-f)

Purpose: To evaluate the dosimetric characteristics of a new formulation of MAGIC gel, called MAGIC-f, which contains the addition of 3.3% formaldehyde, resulting in a gel with increased thermal stability. Methods: MAGIC-f gel was prepared and stored in hermetically sealed plastic containers. After irradiation, magnetic resonance images (MRI) were acquired to evaluate dose and dose distribution. Dosimetric characterization was performed by means of depth dose measurements, dose response sensitivity and linearity, temporal stability, energy and dose rate dependence, dose integration using sequential beams, temperature influence during MRI acquisition and dose distribution integrity. Results: MAGIC-f depth dose measurements are compatible with the dosimetric table data within +/- 4% uncertainty. The dosimeter's R-2 response varies linearly with dose at least from 0 to 6 Gy. The time-course of the sensitivity of the dosimeter following irradiation, indicated stabilization after 2 weeks. The dosimeter's response to irradiation was altered by 6% when increasing the energy from cobalt beams to 10 MV beams. The dose rate dependence of this new formulation of gel dosimeter is small: less than 2.5% for a variation from 200 to 500 cGy/min, and the dependence with the fractionation scheme is about 50% smaller than for standard MAGIC gel, The dependence on scanning temperature was also verified, and the integrity of the dose distribution was confirmed for a period of 90 days. Conclusions: The results demonstrate the applicability of this new dosimeter in tridimensional dose distribution measurements. (C) 2012 Elsevier Ltd. All rights reserved.

Influence of titanium and lutetium on the persistent luminescence of ZrO2

Non-doped as well as titanium and lutetium doped zirconia (ZrO2) materials were synthesized via the sol-gel method and structurally characterized with X-ray powder diffraction. The addition of Ti in the zirconia lattice does not change the crystalline structure whilst the Lu doping introduces a small fraction of the tetragonal phase. The UV excitation results in a bright white-blue luminescence at ca. 500 nm for all the materials which emission could be assigned to the Ti3+ e(g) -> t(2g) transition. The persistent luminescence originates from the same Ti3+ center. The thermoluminescence data shows a well-defined though rather similar defect structures for all the zirconia materials. The kinetics of persistent luminescence was probed with the isothermal decay curve analyses which indicated significant retrapping. The short duration of persistent luminescence was attributed to the quasi-continuum distribution of the traps and to the possibility of shallow traps even below the room temperature. (C) 2012 Optical Society of America

Repression of osteocyte Wnt/beta-catenin signaling is an early event in the progression of renal osteodystrophy

Chronic kidney diseasemineral bone disorder (CKD-MBD) is defined by abnormalities in mineral and hormone metabolism, bone histomorphometric changes, and/or the presence of soft-tissue calcification. Emerging evidence suggests that features of CKD-MBD may occur early in disease progression and are associated with changes in osteocyte function. To identify early changes in bone, we utilized the jck mouse, a genetic model of polycystic kidney disease that exhibits progressive renal disease. At 6 weeks of age, jck mice have normal renal function and no evidence of bone disease but exhibit continual decline in renal function and death by 20 weeks of age, when approximately 40% to 60% of them have vascular calcification. Temporal changes in serum parameters were identified in jck relative to wild-type mice from 6 through 18 weeks of age and were subsequently shown to largely mirror serum changes commonly associated with clinical CKD-MBD. Bone histomorphometry revealed progressive changes associated with increased osteoclast activity and elevated bone formation relative to wild-type mice. To capture the early molecular and cellular events in the progression of CKD-MBD we examined cell-specific pathways associated with bone remodeling at the protein and/or gene expression level. Importantly, a steady increase in the number of cells expressing phosphor-Ser33/37-beta-catenin was observed both in mouse and human bones. Overall repression of Wnt/beta-catenin signaling within osteocytes occurred in conjunction with increased expression of Wnt antagonists (SOST and sFRP4) and genes associated with osteoclast activity, including receptor activator of NF-?B ligand (RANKL). The resulting increase in the RANKL/osteoprotegerin (OPG) ratio correlated with increased osteoclast activity. In late-stage disease, an apparent repression of genes associated with osteoblast function was observed. These data confirm that jck mice develop progressive biochemical changes in CKD-MBD and suggest that repression of the Wnt/beta-catenin pathway is involved in the pathogenesis of renal osteodystrophy. (C) 2012 American Society for Bone and Mineral Research.

DFT and synchrotron radiation study of Eu2+ doped BaAl2O4

The structural distortions resulting from the size mismatch between the Eu2+ luminescent centre and the host Ba2+ cation as well as the electronic structure of BaAl2O4:Eu2+(,Dy3+) were studied using density functional theory (DFT) calculations and synchrotron radiation (SR) luminescence spectroscopy. The modified interionic distances as well as differences in the total energies indicate that Eu2+ prefers the smaller of the two possible Ba sites in the BaAl2O4 host. The calculated Eu2+ 4f(7) and 4f(6)5d(1) ground level energies confirm that the excited electrons can reach easily the conduction band for subsequent trapping. In addition to the green luminescence, a weak blue emission band was observed in BaAl2O4:Eu2+,Dy3+ probably due to the creation of a new Ba2+ site due to the effect of water exposure on the host. (C) 2012 Optical Society of America

Broad combined orange-red emissions from Eu2+- and Eu3+-doped low-silica calcium aluminosilicate glass

In this paper, a broad combined orange-red emission from Eu2+- and Eu3+-doped low-silica calcium aluminosilicate (LSCAS) glass is reported. Spectroscopic results demonstrate that it is possible to tune the emission wavelength by changing the excitation wavelength in the UV-Vis region. The color coordinates for the emission spectra were calculated, and using the Commission Internationale de l'Eclairage 1931 and 1976 chromatic diagrams, it is possible to note that they are dependent on the excitation wavelength. In addition, the (u', v') color coordinates for the investigated LSCAS samples are close to the Planckian spectrum in the cold region between 2000 and 2600K. Our results show that the Eu:LSCAS system can be used in a white light phosphor when mixed in aggregate with phosphors using green-yellow luminescent ions. (c) 2012 Optical Society of America

DNA damage profiles induced by sunlight at different latitudes

Despite growing knowledge on the biological effects of ultraviolet (UV) radiation on human health and ecosystems, it is still difficult to predict the negative impacts of the increasing incidence of solar UV radiation in a scenario of global warming and climate changes. Hence, the development and application of DNA-based biological sensors to monitor the solar UV radiation under different environmental conditions is of increasing importance. With a mind to rendering a molecular view-point of the genotoxic impact of sunlight, field experiments were undertaken with a DNA-dosimeter system in parallel with physical photometry of solar UVB/UVA radiation, at various latitudes in South America. Onapplying biochemical and immunological approaches based on specific DNA-repair enzymes and antibodies, for evaluating sunlight-induced DNA damage profiles, it became clear that the genotoxic potential of sunlight does indeed vary according to latitude. Notwithstanding, while induction of oxidized DNA bases is directly dependent on an increase in latitude, the generation of 6-4PPs is inversely so, whereby the latter can be regarded as a biomolecular marker of UVB incidence. This molecular DNA lesion-pattern largely reflects the relative incidence of UVA and UVB energy at any specific latitude. Hereby is demonstrated the applicability of this DNA-based biosensor for additional, continuous field experiments, as a means of registering variations in the genotoxic impact of solar UV radiation. Environ. Mol. Mutagen. 2012. (c) 2012 Wiley Periodicals, Inc.

Synthesis and Characterization of Gold/Alanine Nanocomposites with Potential Properties for Medical Application as Radiation Sensors

Radiation dose assessment is essential for several medical treatments and diagnostic procedures. In this context, nanotechnology has been used in the development of improved radiation sensors, with higher sensitivity as well as smaller sizes and energy dependence. This paper deals with the synthesis and characterization of gold/alanine nanocomposites with varying mass percentage of gold, for application as radiation sensors. Alanine is an excellent stabilizing agent for gold nanoparticles because the size of the nanoparticles does not augment with increasing mass percentage of gold, as evidenced by UV-vis spectroscopy, dynamic light scattering, and transmission electron microscopy. X-ray diffraction patterns suggest that the alanine crystalline orientation undergoes alterations upon the addition of gold nanoparticles. Fourier transform infrared spectroscopy indicates that there is interaction between the gold nanoparticles and the amine group of the alanine molecules, which may be the reason for the enhanced stability of the nanocomposite. The application of the nanocomposites as radiation detectors was evaluated by the electron spin resonance technique. The sensitivity is improved almost 3 times in the case of the nanocomposite containing 3% (w/w) gold, so it can be easily tuned by changing the amount of gold nanoparticles in the nanocomposites, without the size of the nanoparticles influencing the radiation absorption. In conclusion, the featured properties, such as homogeneity, nanoparticle size stability, and enhanced sensitivity, make these nanocomposites potential candidates for the construction of small-sized radiation sensors with tunable sensitivity for application in several medical procedures.

Comparison of different dosimetric methods for red marrow absorbed dose calculation in thyroid cancer therapy

Several dosimetric methods have been proposed for estimating red marrow absorbed dose (RMAD) when radionuclide therapy is planned for differentiated thyroid cancer, although to date, there is no consensus as to whether dose calculation should be based on blood-activity concentration or not. Our purpose was to compare RMADs derived from methods that require collecting patients' blood samples versus those involving OLINDA/EXM software, thereby precluding this invasive procedure. This is a retrospective study that included 34 patients under treatment for metastatic thyroid disease. A deviation of 10 between RMADs was found, when comparing the doses from the most usual invasive dosimetric methods and those from OLINDA/EXM. No statistical difference between the methods was discovered, whereby the need for invasive procedures when calculating the dose is questioned. The use of OLINDA/EXM in clinical routine could possibly diminish data collection, thus giving rise to a simultaneous reduction in time and clinical costs, besides avoiding any kind of discomfort on the part of the patients involved.

Quartz OSL sensitivity as a proxy for storm activity on the southern Brazilian coast during the Late Holocene

Natural cycles of irradiation during burial and bleaching due to solar exposure during transport increase the Optically Stimulated Luminescence (OSL) sensitivity of quartz sand grains. The relationship between the OSL sensitivity and sediment transport allows to discriminate quartz sand grains with different depositional histories. In this paper, we evaluate the variation of OSL sensitivity in quartz grains deposited during the progradation of the Ilha Comprida barrier on the southern Brazilian, coast. Changes in sand sensitivity recorded by barrier growth since 6 ka ago are controlled by the variation in the proportion of low versus high sensitivity quartz grains. Low sensitivity grains with short sedimentary history are supplied by the Ribeira de Iguape River and reach the barrier through southward alongshore currents during fair weather conditions. Storm conditions shift the alongshore currents to northeast and permit the transport of high sensitivity grains with long sedimentary history from distal southern coastal sectors to the barrier. Therefore, the input of distal sediments for the Ilha Comprida barrier depends on the frequency and intensity of storms. Thus, the OSL sensitivity can be used as proxy for storm activity. The variation of OSL sensitivity through time indicates that the Ilha Comprida barrier changed from a relatively stable to an unstable storm pattern around 2 ka ago. Periods with increased storm activity peaked around AD 500, AD 1500 and AD 1850, approximately on the boundaries of the Medieval Climate Anomaly and the Little Ice Age. (C) 2012 Elsevier B.V. All rights reserved.