Identification of defect centers responsible for thermoluminescence emission in sol-gel synthesized calcium silicate phosphor.

The thermoluminescence (TL) of calcium silicate phosphor (CSO) prepared by the sol-gel method and sintered at 1200 °C were investigated. From Tm-Tstop curve, TL emission spectrum and computer deconvolution using electron traps with discrete and continuous distributions, the glow curves were found to be composed of four TL peaks (117, 190, 250 and 275 °C) with a single emission band centered at 370 nm. Electron paramagnetic resonance (EPR) investigation has been carried out to identify the defect centers formed in the CSO phosphor by γ-irradiation and find the centers related to the TL process in the phosphor. At room temperature, three defect centers were observed. The first center, characterized by the principal g-values of 2.014, 2.011, and 2.0080 was assigned to an O- ion. The second center with g-values 2.015, 2.013, and 2.010 is also attributed to an O- ion and is associated with the TL peak at 280 °C. The third center, with an isotropic g-value of 2.0011 was identified as the F+ center (singly ionized oxygen vacancy) and relates to the TL peak at 280 °C.

Chemical contamination in coastal areas alters shape, resistance and composition of carnivorous gastropod shells.

Morphological, structural and compositional alterations in shells of molluscs have been proposed as putative biomarkers of chemical contamination in coastal zones. Despite this, few studies were carried out using top predator gastropods which tend to be more susceptible to contamination exposure. Thus, the present study assessed disturbances on shells of Stramonita brasiliensis considering compression resistance and organic and mineralogical matrix composition, related to morphometric alterations. Results showed reductions in compression resistance and organic matrix content associated with higher contaminated sites. In addition, a predominance of calcite polymorphs was seen in shells obtained in polluted areas. Such outputs were consistent with local contamination levels which may have induced the observed alterations. Thus, changes in mollusc shells showed good performance as potential biomarkers of coastal contamination, being probably observed in other species of carnivorous gastropods around the world.

Identification of ESR centers and their role in the TL of natural salt from Lluta, Peru.

In this study, the thermoluminescence (TL) properties of natural NaCl from Lluta, Arequipa-Peru was investigated. The number of peaks and the kinetic parameters associated with the TL glow peaks of NaCl sample after gamma-irradiation were analyzed by initial rise and deconvolution method. Defect centers induced in pure salt by gamma irradiation have been studied by electron spin resonance (ESR) with a view to identify the centers associated with the TL process in the salt. Thermal annealing experiments indicate the presence of three defect centers. Center I characterized by the g-value 2.011 is identified as an O- ion and relates with the dominant TL peak at 220 °C. Center II with a g-value of 2.0058 is attributed to a F center and is found to correlate with the 128 °C TL peak. Center III has of g-value 2.014 and is also assigned to an O- ion.

Rathke's cleft cyst infections and pituitary abscesses: case series and review of the literature.

PURPOSE: Pituitary abscesses (PAs) are a rare clinical entity which may arise from normal pituitary tissue or underlying lesions within the gland. Rathke's cleft cysts (RCCs) are not commonly associated with the development of PA. METHODS: Retrospective chart review of three patients with PAs within RCCs at a single university center and review of the literature. RESULTS: Three cases are reported. The first case presented with fever and headache and a history of prior surgery due to RCC and a recent respiratory tract infection. The second case had a history of recent skin infections and presented with sudden onset headache and hypopituitarism. In the third case, chronic visual field impairment prompted an ophthalmologic evaluation resulting in a diagnosis of an adenoma and an infected RCC. In all three cases, an endoscopic endonasal approach was performed to drain infected tissue and allowed microbiological identification of gram-positive cocci, followed by treatment with antibiotics for at least three weeks. Cases in the literature are scarce and the diagnosis is usually made intraoperatively due to non-specific manifestations and imaging. PAs arising from underlying pituitary lesions are less common than primary PAs. Differential diagnosis should include pituitary apoplexy, hypophysitis and other cystic lesions. CONCLUSION: PAs occurring in RCCs are infrequent. Clinical manifestations are commonly subacute, without septic symptoms. Imaging is usually non-specific. Preoperative diagnosis is infrequent and a broad differential diagnosis should be considered. Empirical antimicrobial therapy should be initiated and adjusted after obtaining cultures to reduce the rate of recurrence and improve clinical outcomes.

Dating and determination of firing temperature of ancient potteries from Yumina archaeological site, Arequipa, Peru.

Pottery fragments from the Yumina archaeological site, Arequipa, Peru, were dated by means of thermoluminescence (TL) and optically stimulated luminescence (OSL). Electron paramagnetic resonance (EPR) technique was used to study the firing temperature using the iron signal (Fe3+) as a firing temperature reference. The ages of the samples were found to be between 1190 ±â€¯30 and 1240 ±â€¯80 years (777 ±â€¯80 and 827 ±â€¯30 A.D.) determined by both techniques. The firing temperature of ceramics was found to be around 550  ± 50 °C. Our study, based on the combination of TL and OSL techniques to study Yumina archaeological site pottery, will be helpful for archaeologists in Peru. With the results of this investigation, we can understand the chronology and determine the areas of dispersion and density of the archaeological occupation in the Arequipa Valley. In addition, the calculated ages are consistent with the occupation period of the Yumina archaeological site estimated by stratigraphic analysis of the potteries.

Dating of carbonate covering cave paintings at peruaçu, Brazil by TL and EPR methods.

In the present work, carbonate samples covering wall painting of four points in the same site found at Peruaçu National Park in the extreme northwest of the state of Minas Gerais, Brazil, has been investigated and dated by thermoluminescence (TL) and electron paramagnetic resonance (EPR) techniques. The EPR spectrum of the carbonate samples presented the typical six signals due to Mn2+ ion and signals around g~2.0 due to SO2- and CO2-. The thermal stability and dose response of the EPR signals were found to be suitable for an age determination using the center due to CO2-. The carbonate sample exhibits TL peaks at approximately 350 °C. TL and EPR dating of the carbonate samples that covered the cave paintings gave an age of 33.13 to 48.40 ka. This series of dating data indicate that in the region about 220-250 km from the coast and extending from the State of Piaui, Bahia to Minas Gerais people lived around 50000 years ago.

Experimental and theoretical structural/spectroscopical correlation of enterobactin and catecholamide.

Here we report the IR spectra of FeEnterobactin in catecholate conformations ([CatFeEB]3-) obtained by DFT calculations using PBE/QZVP and their correlation it with its experimental counterpart [SalH3FeEB]0. Fragments of FeEnterobactin and Enterobactin (H6EB) are elucidated from their MALDI-TOF mass spectrometry, and the dependence of the frontier orbitals (HOMO and LUMO) with the catecholamide dihedral angles of H6EB is reported. The frequency distribution of catecholamide dihedral angle of H6EB was carried-out using molecular dynamics (MD). The data presented enriches the understanding of [CatFeEB]3 - and H6EB frequency distribution and reactivity.

Experimental and Computational Characterization of the Interaction between Gold Nanoparticles and Polyamidoamine Dendrimers.

Dendrimers provide a means to control the synthesis of gold nanoparticles and stabilize their suspensions. However, design of improved dendrimers for this application is hindered by a lack of understanding how the dendrimers and synthesis conditions determine nanoparticle morphology and suspension stability. In the present work, we evaluate the effect of polyamidoamine (PAMAM) dendrimers terminated with different functional groups (-OH or -NH3+) and different synthesis conditions on the morphology of the resulting gold nanoparticles and their stability in solution. We leverage molecular dynamics (MD) simulations to identify the atomic interactions that underlie adsorption of PAMAM dendrimers to gold surface and how the thermodynamics of this adsorption depends on the terminal functional groups of the dendrimers. We find that gold nanoparticles formed with hydroxyl-terminated PAMAM (PAMAM-OH) rapidly aggregate, whereas those formed with PAMAM-NH3+ are stable in solution for months of storage. Synthesis under ultrasound sonication is shown to be more rapid than that under agitation, with sonication producing smaller nanoparticles. Free-energy calculations in MD simulations show that all dendrimers have a high affinity for the gold surface, although PAMAM-OH and its oxidized aldehyde form (PAMAM-CHO) have a greater affinity for the nanoparticle surface than PAMAM-NH3+. Although adsorption of PAMAM-OH and PAMAM-CHO has both favorable entropy and enthalpy, adsorption of PAMAM-NH3+ is driven by a strong enthalpic component subject to an unfavorable entropic component.

IR and NMR spectroscopic correlation of enterobactin by DFT.

Emerging and re-emerging epidemic diseases pose an ongoing threat to global health. Currently, Enterobactin and Enterobactin derivatives have gained interest, owing to their potential application in the pharmaceutical field. As it is known [J. Am. Chem. Soc (1979) 101, 20, 6097-6104], Enterobactin (H6EB) is an efficient iron carrier synthesized and secreted by many microbial species. In order to facilitate the elucidation of enterobactin and its analogues, here we propose the creation of a H6EB standard set using Density Functional Theory Infrared (IR) and NMR spectra. We used two exchange-correlation (xc) functionals (PBE including long-range corrections LC-PBE and mPW1), 2 basis sets (QZVP and 6-31G(d)) and 2 grids (fine and ultrafine) for most of the H6EB structures dependent of dihedral angles. The results show a significant difference between the OH and NH bands, while the CO amide and O(CO) IR bands are often found on top of each other. The NMR DFT calculations show a strong dependence on the xc functional, basis set, and grid used for the H6EB structure. Calculated 1H and 13C NMR spectra enable the effect of the solvent to be understood in the context of the experimental measurements. The good agreement between the experimental and the calculated spectra using LC-PBE/QZVP and ultrafine grid suggest the possibility of the systems reported here to be considered as a standard set. The dependence of electrostatic potential and frontier orbitals with the catecholamide dihedral angles of H6EB is described. The matrix-assisted laser desorption/ionization time of the flight mass spectrometry (MALDI-TOF MS) of H6EB is also reported of manner to enrich the knowledge about its reactivity.

Synthesis, thermoluminescence, defect center and dosimetric characteristics of LiF:Mg,Cu,P,Si phosphor.

LiF:Mg,Cu,P,Si (MCPS), a new tissue equivalent phosphor, was synthesized by solid state method. Powder x-ray diffraction and scanning electron microscope were employed to determine the structural features. The dosimetric characteristics, electron spin resonance (ESR) and defect centers of this newly prepared phosphor were investigated. The MCPS phosphor is highly sensitive when compared with LiF:Mg,Ti and LiF:Mg,Cu,P (MCP), with the TL sensitivity being 35 times and 1.3 times higher respectively. The dosimetric peak occurs at 220°C with a well defined glow curve structure similar to MCP. MCPS phosphor shows a linear dose response till 10Gy. The minimum detectable dose has been found to be 8µGy. The thermal stability of the phosphor could be enhanced by 20°C from 240°C to 260°C when compared to MCP. Defect centers formed in the phosphor by gamma irradiation have been studied by ESR to identify the centers associated with the TL process in this phosphor. Thermal annealing experiments reveal the presence of several defect centers. Center I which shows an isotropic g factor of 2.0233 has been found to relate with the TL peaks at 160°C, 220°C and 265°C. Centers II and III are characterized by isotropic g values of 2.0096 and 2.0019 respectively and are attributed to F centers.

Synthesis and Study of Fe-Doped Bi2S3 Semimagnetic Nanocrystals Embedded in a Glass Matrix.

Iron-doped bismuth sulphide (Bi2-xFexS3) nanocrystals have been successfully synthesized in a glass matrix using the fusion method. Transmission electron microscopy images and energy dispersive spectroscopy data clearly show that nanocrystals are formed with an average diameter of 7-9 nm, depending on the thermic treatment time, and contain Fe in their chemical composition. Magnetic force microscopy measurements show magnetic phase contrast patterns, providing further evidence of Fe incorporation in the nanocrystal structure. The electron paramagnetic resonance spectra displayed Fe3+ typical characteristics, with spin of 5/2 in the 3d5 electronic state, thereby confirming the expected trivalent state of Fe ions in the Bi2S3 host structure. Results from the spin polarized density functional theory simulations, for the bulk Fe-doped Bi2S3 counterpart, corroborate the experimental fact that the volume of the unit cell decreases with Fe substitutionally doping at Bi1 and Bi2 sites. The Bader charge analysis indicated a pseudo valency charge of 1.322|e| on FeBi1 and 1.306|e| on FeBi2 ions, and a spin contribution for the magnetic moment of 5.0 µB per unit cell containing one Fe atom. Electronic band structures showed that the (indirect) band gap changes from 1.17 eV for Bi2S3 bulk to 0.71 eV (0.74 eV) for Bi2S3:FeBi1 (Bi2S3:FeBi2). These results are compatible with the 3d5 high-spin state of Fe3+, and are in agreement with the experimental results, within the density functional theory accuracy.

Dating stalagmite from Caverna do Diabo (Devil´S Cave) by TL and EPR techniques.

A cylindrical fragment of stalagmite from Caverna do Diabo, State of São Paulo, Brazil, has been studied and dated by thermoluminescence and electron paramagnetic resonance techniques. The thermoluminescence glow curves of stalagmite samples and subsequently gamma irradiated, have shown rise of three peaks at 135, 180 and 265 °C. From electron paramagnetic resonance spectra of stalagmite was possible to clearly identify three paramagnetic centers in the g = 2.0 region: Centers I, II and III are due to , and , respectively. The additive method was applied to calculate the accumulated dose using thermoluminescence peak at 265 °C and the electron paramagnetic resonance signal at g = 1.9973 of CO- 2 radical. The ages of the different slices of stalagmite were determined from the Dac- values and Dan- value, obtaining an average of 86410 for central slice, 53421 for second slice, 31490 for third slice and 46390 years B.P. for the central region of upper end.

Revision of the genus Paralipsis Foerster, 1863 (Hymenoptera, Braconidae), with the description of two new species.

The Palaearctic genus Paralipsis Foerster, 1863 (Hymenoptera: Braconidae: Aphidiinae) is revised and two new species are described: Paralipsis tibiator van Achterberg & Ortiz de Zugasti, sp. n. from Spain and Paralipsis planus van Achterberg, sp. n. from the Netherlands. Some biological notes are supplied for Paralipsis tibiator sp. n. A key to the four known species is added and all species are illustrated.

Mechanistic Studies on the Self-Assembly of PLGA Patchy Particles and Their Potential Applications in Biomedical Imaging.

Currently, several challenges prevent poly(lactic-co-glycolic acid) (PLGA) particles from reaching clinical settings. Among these is a lack of understanding of the molecular mechanisms involved in the formation of these particles. We have been studying in depth the formation of patchy polymeric particles. These particles are made of PLGA and lipid-polymer functional groups. They have unique patch-core-shell structural features: hollow or solid hydrophobic cores and a patchy surface. Previously, we identified the shear stress as the most important parameter in a patchy particle's formation. Here, we investigated in detail the role of shear stress in the patchy particle's internal and external structure using an integrative experimental and computational approach. By cross-sectioning the multipatch particles, we found lipid-based structures embedded in the entire PLGA matrix, which represents a unique finding in the PLGA field. By developing novel computational fluid dynamics and molecular dynamics simulations, we found that the shear stress determines the internal structure of the patchy particles. Equally important, we discovered that these particles emit a photoacoustic (PA) signal in the optical clinical imaging window. Our results show that particles with multiple patches emit a higher PA signal than single-patch particles. This phenomenon most likely is due to the fact that multipatchy particles absorb more heat than single-patchy particles as shown by differential scanning calorimetry analysis. Furthermore, we demonstrated the use of patchy polymeric particles as photoacoustic molecular probes both in vitro and in vivo studies. The fundamental studies described here will help us to design more effective PLGA carriers for a number of medical applications as well as to accelerate their medical translation.

Radiation dosimetry using decreasing TL intensity in a few variety of silicate crystals.

This study shows that there are some ionic crystals which after irradiation with high gamma dose Dm and subsequent irradiation with low doses ranging up to 500Gy present a decreasing TL intensity as dose increases. This interesting feature can be used as a calibration curve in radiation dosimetry. Such behavior can be found in green quartz, three varieties of beryl and pink tourmaline. In all these silicate crystals it can be shown that irradiation with increasing γ-dose there is a dose Dm for which the TL intensity is maximum. Of course, Dm varies depending on the crystal and irradiated crystal with the dose Dm is stable. If one of these crystals is taken and irradiated with doses from low values up to 400-500Gy, a curve of decreasing TL intensity is obtained; such a curve can be used as a calibration curve.

PAMAM G4 dendrimers as inhibitors of the iron storage properties of human L-chain ferritin.

Cationic dendrimers, such as PAMAM, are known to be positively charged at neutral pH allowing their unspecific interaction with proteins and other cellular components. Especially, ferritin, which has an important role in iron homeostasis, presents a negative electrostatic potential at the 3-fold channel. This channel is important in the functionality of ferritin because it allows the iron entry into its inner cavity. In this way, the interaction between the protonated terminal amines of the dendrimer and the negatively charged 3-fold channels of ferritin is expected. Experimental measurements demonstrated that PAMAM G4 inhibits the iron storage properties of L-chain human ferritin (L-Ftn). Molecular dynamics simulations have been used to analyze the specific interaction between PAMAM G4 and L-Ftn. Results show that PAMAM G4 effectively interacts with the 3-fold channels of L-Ftn, suggesting that this interaction is responsible for the inhibition of the iron storage properties of L-Ftn.

Study of luminescence, color and paramagnetic centers properties of albite.

A sample of natural albite, NaAlSi3O8, from the state of Minas Gerais, Brazil, has been investigated. The mineral is a solid solution of K-feldspar (4600 ppm--K) and Ca-feldspar (1100 ppm--Ca). The TL spectra of natural and the pre-annealed at high temperature albite presented a very intense band around 275 nm and weaker bands around 400 and 560 nm. Other TL properties have been investigated through monochromatic (275 nm and 400 nm) glow curves. The EPR spectrum measured at low temperature (77K) shows the typical 11 lines signal due to Al-O(-)-Al center superposed on Fe(3+) signal around g=2.0. The EPR spectra above 260 K show only g=2.0 signal due to Fe(3+) ions.

Synthesis and characterization of an insoluble polymer based on polyamidoamine: applications for the decontamination of metals in aqueous systems.

We present a novel, insoluble, low-generation polyamidoamine (PAMAM)-based polymer. The monomer and polymer were characterized by fourier transform infrared spectroscopy, electrospray ionization mass spectrometry and thermogravimetric measurement, revealing that G0 acryloyl-terminated PAMAM were synthesized and polymerized using ammonium persulfate as an initiator, producing a high-density PAMAM derivative (PAMAM-HD). PAMAM-HD was tested for its ability to remove Na(I), K(I), Ca(II), Mg(II), Cu(II), Mn(II), Cd(II), Pb(II) and Zn(II) ions from acidic, neutral and basic aqueous solutions. PAMAM-HD efficiently removed metals ions from all three solutions. The greatest absorption efficiency at neutral pH was observed against Cu(II), Cd(II) and Pb(II), and the experimental data were supported by the calculated Kd values. Our data could have a significant impact on water purification by providing an inexpensive and efficient polymer for the removal of metal ions.

Identification and functional expression of a glutamate- and avermectin-gated chloride channel from Caligus rogercresseyi, a southern Hemisphere sea louse affecting farmed fish.

Parasitic sea lice represent a major sanitary threat to marine salmonid aquaculture, an industry accounting for 7% of world fish production. Caligus rogercresseyi is the principal sea louse species infesting farmed salmon and trout in the southern hemisphere. Most effective control of Caligus has been obtained with macrocyclic lactones (MLs) ivermectin and emamectin. These drugs target glutamate-gated chloride channels (GluCl) and act as irreversible non-competitive agonists causing neuronal inhibition, paralysis and death of the parasite. Here we report the cloning of a full-length CrGluClα receptor from Caligus rogercresseyi. Expression in Xenopus oocytes and electrophysiological assays show that CrGluClα is activated by glutamate and mediates chloride currents blocked by the ligand-gated anion channel inhibitor picrotoxin. Both ivermectin and emamectin activate CrGluClα in the absence of glutamate. The effects are irreversible and occur with an EC(50) value of around 200 nM, being cooperative (n(H) = 2) for ivermectin but not for emamectin. Using the three-dimensional structure of a GluClα from Caenorabditis elegans, the only available for any eukaryotic ligand-gated anion channel, we have constructed a homology model for CrGluClα. Docking and molecular dynamics calculations reveal the way in which ivermectin and emamectin interact with CrGluClα. Both drugs intercalate between transmembrane domains M1 and M3 of neighbouring subunits of a pentameric structure. The structure displays three H-bonds involved in this interaction, but despite similarity in structure only of two these are conserved from the C. elegans crystal binding site. Our data strongly suggest that CrGluClα is an important target for avermectins used in the treatment of sea louse infestation in farmed salmonids and open the way for ascertaining a possible mechanism of increasing resistance to MLs in aquaculture industry. Molecular modeling could help in the design of new, more efficient drugs whilst functional expression of the receptor allows a first stage of testing of their efficacy.

Nanoinformatics: developing new computing applications for nanomedicine.

Nanoinformatics has recently emerged to address the need of computing applications at the nano level. In this regard, the authors have participated in various initiatives to identify its concepts, foundations and challenges. While nanomaterials open up the possibility for developing new devices in many industrial and scientific areas, they also offer breakthrough perspectives for the prevention, diagnosis and treatment of diseases. In this paper, we analyze the different aspects of nanoinformatics and suggest five research topics to help catalyze new research and development in the area, particularly focused on nanomedicine. We also encompass the use of informatics to further the biological and clinical applications of basic research in nanoscience and nanotechnology, and the related concept of an extended "nanotype" to coalesce information related to nanoparticles. We suggest how nanoinformatics could accelerate developments in nanomedicine, similarly to what happened with the Human Genome and other -omics projects, on issues like exchanging modeling and simulation methods and tools, linking toxicity information to clinical and personal databases or developing new approaches for scientific ontologies, among many others.