Unravelling the Chemical Morphology of a Mesoporous Titanium Dioxide Interface by Confocal Raman Microscopy: New Clues for Improving the Efficiency of Dye Solar Cells and Photocatalysts

The presence of anatase and rutile domains on nanocrystalline films of P25 TiO(2), as well as the distinct coordination modes of carboxylates on those phases, were revealed by confocal Raman microscopy, a technique that showed to be suitable for imaging the chemical morphology down to submicrometric size.

Quenching of Photoactivity in Phthalocyanine Copper(II)-Titanate Nanotube Hybrid Systems

Titanate nanotubes (TiNTs) were obtained by hydrothermal treatment of anatase powder in aqueous NaOH solution and then modified with 2,9,16,23-tertracarboxyl phthalocyanine copper(H) (CuPc). This hybrid organic inorganic nanoscopic system was characterized by X-ray diffraction, microscopy, and spectroscopy. Transmission electron microscopy (TEM) images of pure and modified TiNTs revealed multiwall structures with an average outer diameter of 9 nm and a length of several hundred nanometers. The tubular morphology of the TiNTs was covered with CuPc-film. The amount of CuPc adsorbed onto the TiNTs was quantified by electron paramagnetic resonance (EPR). Using the same technique and spin-trapping methodology, the photogeneration of reactive oxygen species (ROS) from the TiNTs was systematically investigated. A drastic quenching of photoactivity was observed in the CuPc/TiNT hybrid system. Electron transfer from excited CuPc states to the TiNT conduction band followed by electron recombination may be the cause of this quenching.

Oxindole-Schiff base copper(II) complexes interactions with human serum albumin: Spectroscopic, oxidative damage, and computational studies

CD and EPR were used to characterize interactions of oxindole-Schiff base copper(II) complexes with human serum albumin (HSA). These imine ligands form very stable complexes with copper, and can efficiently compete for this metal ion towards the specific N-terminal binding site of the protein, consisting of the amino acid sequence Asp-Ala-His. Relative stability constants for the corresponding complexes were estimated from CD data, using the protein as competitive ligand, with values of log K(CuL) in the range 15.7-18.1, very close to that of [Cu(HSA)] itself, with log K(CuHSA) 16.2. Some of the complexes are also able to interfere in the a-helix structure of the protein, while others seem not to affect it. EPR spectra corroborate those results, indicating at least two different metal species in solution, depending on the imine ligand. Oxidative damage to the protein after incubation with these copper(II) complexes, particularly in the presence of hydrogen peroxide, was monitored by carbonyl groups formation, and was observed to be more severe when conformational features of the protein were modified. Complementary EPR spin-trapping data indicated significant formation of hydroxyl and carbon centered radicals, consistent with an oxidative mechanism. Theoretical calculations at density functional theory (DFT) level were employed to evaluate Cu(II)-L binding energies, L -> Cu(II) donation, and Cu(II) -> L back-donation, by considering the Schiff bases and the N-terminal site of HSA as ligands. These results complement previous studies on cytotoxicity, nuclease and pro-apoptotic properties of this kind of copper(II) complexes, providing additional information about their possibilities of transport and disposition in blood plasma. (C) 2009 Elsevier Inc. All rights reserved.

Genetic differentiation between sympatric populations of Bacillus cereus and Bacillus thuringiensis

Little is known about genetic exchanges in natural populations of bacteria of the spore-forming Bacillus cereus group, because no population genetics studies have been performed with local sympatric populations. We isolated strains of Bacillus thuringiensis and B. cereus from small samples of soil collected at the same time from two separate geographical sites, one within the forest and the other at the edge of the forest. A total of 100 B. cercus and 98 B. thuringiensis strains were isolated and characterized by electrophoresis to determine allelic composition at nine enzymatic loci. We observed genetic differentiation between populations of B. cereus and B. thuringiensis. Populations of a given Bacillus species-B. thuringiensis or B. cereus-were genetically more similar to each other than to populations of the other Bacillus species. Hemolytic activity provided further evidence of this genetic divergence, which remained evident even if putative clones were removed from the data set. Our results suggest that the rate of gene flow was higher between strains of the same species, but that exchanges between B. cereus and B. thuringiensis were nonetheless possible. Linkage disequilibrium analysis revealed sufficient recombination for B. cereus populations to be considered panmictic units. In B. thuringiensis, the balance between clonal proliferation and recombination seemed to depend on location. Overall, our data indicate that it is not important for risk assessment purposes to determine whether B. cereus and B. thuringiensis belong to a single or two species. Assessment of the biosafety of pest control based on B. thuringiensis requires evaluation of the extent of genetic exchange between strains in realistic natural conditions.

On the origin of exciton formation in dye doped Alq(3) OLEDs

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Photo-induced electron trapping in indirect bandgap AlxGa1-xAs : Si at low temperature

A variation of photoconductivity excitation with wavelength is applied to Si-doped Al0.56Ga0.44As (indirect bandgap material) for a wide range of temperature. The lower the temperature the lower the photocurrent below 70 K. In the range 13-30 K there is a decrease in the photoconductivity spectrum slightly above the bandgap transition energy, followed by another increase in the conductivity. We interpret these results in the light of existing models and confirm the trapping by the X-valley effective mass state. which is responsible for attenuation of persistent photoconductivity below 70 K. A DX0 intermediate state which has non-negligible lifetime is proposed as responsible for the decrease in the photoconductivity with about 561 nm of wavelength of exciting light, in the investigated 13-30 g range.

Trapping neutral fermions with kink-like potentials

The intrinsically relativistic problem of neutral fermions subject to kink-like potentials (similar to tanh gamma x) is investigated and the exact bound-state solutions are found. Apart from the lonely hump solutions for E = +/- mc(2), the problem is mapped into the exactly solvable Sturm-Liouville problem with a modified Poschl-Teller potential. An apparent paradox concerning the uncertainty principle is solved by resorting to the concepts of effective mass and effective Compton wavelength. (c) 2005 Elsevier B.V. All rights reserved.

Effect of electron magnetic trapping in a plasma immersion ion implantation system

In this work we describe a two-dimensional computer simulation of magnetic field enhanced plasma immersion implantation system. Negative bias voltage of 10.0 kV is applied to a cylindrical target located on the axis of a grounded vacuum chamber filled with uniform nitrogen plasma. A pair of external coils creates a static magnetic field with main vector component along the axial direction. Thus, a system of crossed ExB field is generated inside the vessel forcing plasma electrons to rotate in azimuthal direction. In addition, the axial variation of the magnetic field intensity produces magnetic mirror effect that enables axial particle confinement. It is found that high-density plasma regions are formed around the target due to intense background gas ionization by the trapped electrons. Effect of the magnetic field on the sheath dynamics and the implantation current density of the PIII system is investigated. By changing the magnetic field axial profile (varying coils separation) an enhancement of about 30% of the retained dose can be achieved. The results of the simulation show that the magnetic mirror configuration brings additional benefits to the PIII process, permitting more precise control of the implanted dose.

Bark and ambrosia beetle (Coleoptera : Scolytidae) responses to volatiles from aging loblolly pine billets

Many species of bark and ambrosia beetles use host volatiles as cues for breeding site location. In a study where the objectives were to identify the different volatiles released by Pinus taeda L. billets as they age, to determine the arrival sequence of scolytids (Colcoptera: Scolytidae), and to correlate volatile emission by the billets with beetle catches, 25 species of scolytids were trapped. Bark beetles were more attracted to the billets in the beginning of the period. whereas ambrosia beetles arrived later. Among the bark beetles, Dendroctonus terebrans (Olivier) was significantly more attracted during the Ist 3 wk after tree felling, Hylastes tenuis Eichhoff in the Ist 2 wk. Pityophtorus pulicarius (Zimmermann) in weeks 2 and 3, and Ips grandicollis (Eichhoff) was more attracted on weeks 3 and 4. Among the ambrosia beetles, Xyleborinus saxeseni (Ratzeburg) was more attracted to billets during weeks 4-6, whereas Xyleborus pubescens Zimmermann and Xyleborus californicus Wood were more attracted during week 6. The billets showed marked decline in attractiveness to all scolytids after 8 wk. Volatiles collected during the beetle trapping periods included 15 hydrocarbon monoterpenes, 18 oxygenated monoterpenes, 4-allylanisole, and ethanol. The hydrocarbon monoterpenes and 4-allylanisole decreased sharply over time, but oxygenated monoterpenes and ethanol increased up to weeks 4-6, after which they also decreased. Good correlations between certain billet volatiles and catches for some beetle species were obtained, but their biological significance could not be determined.

Divergence Between Sympatric Rice- and Maize-Infecting Populations of Rhizoctonia solani AG-1 IA from Latin America

The basidiomycetous fungus, Rhizoctonia solani anastomosis group (AG)-1 IA is a major pathogen in Latin America causing sheath blight (SB) of rice Particularly in Venezuela. the fungus also Causes banded leaf and sheath blight (BLSB) oil maize, which is considered all emerging disease problem where maize replaced traditional rice-cropping areas or is now planted in adjacent. fields Our goals in this study Were 10 elucidate (i) the effects of host specialization on gene flow between sympatric and allopatric rice and maize-infecting fungal populations and (ii) the reproductive mode of the fungus, looking for evidence of recombination in total, 375 isolates of R. solani AG1 IA sampled from three sympatric rice and maize fields in Venezuela (Porutuguesa State) and two allopatric rice fields from Colombia (Meta State) and Panama (Chiriqui State) were genotyped Using, 10 microsatellite loci Allopatric populations from Venezuela. Colombia. and Panama were significantly differentiated (Phi(ST), of 0 16 to 0 34). Partitioning of the genetic diversity indicated differentiation between sympatric populations from different host species, with 17% of the total genetic variation distributed between hosts while only 3 to 6% wits distributed geographically among the sympatric Venezuelan Fields We detected symmetrical historical migration between the rice- and the maize-infecting populations from Venezuela Rice- and maize-derived isolates were able to infect built rice and maize but were more aggressive Oil their original hosts, consistent with host specialization. Because the maize- and rice-infecting populations are still cross-pathogenic, we postulate that the genetic differentiation was relatively recent and mediated via a host shift. An isolation with nu.-ration analysis indicated that the maize-infecting population diverged from the rice-infecting population between 40 and 240 years ago Our findings also suggest that maize-infecting Populations have a mainly recombining reproductive system whereas the rice-infecting Populations have a Mixed reproductive system in Latin America

GIANT FUSIFORM ANEURYSM ARISING FROM FENESTRATED POSTERIOR CEREBRAL ARTERY and BASILAR TIP VARIATION: CASE REPORT

OBJECTIVE: A giant fusiform aneurysm in the posterior cerebral artery (PCA) is rare, as is fenestration of the PCA and basilar apex variation. We describe the angiographic and surgical findings of a giant fusiform aneurysm in the P1-P2 PCA segment associated with PCA bilateral fenestration and superior cerebellar artery double origin.CLINICAL PRESENTATION: A 26-year-old woman presented with a 2-month history of visual blurring. Digital subtraction angiography showed a giant (2.5 cm) fusiform PCA aneurysm in the right P1-P2 segment. The 3-dimensional view showed a caudal fusion pattern from the upper portion of the basilar artery associated with a bilateral long fenestration of the P1 and P2 segments and superior cerebellar artery double origin.INTERVENTION: Surgical trapping of the right P1 -P2 segment, including the posterior communicating artery, was performed by a pretemporal approach. Angiograms performed 3 and 13 months after surgery showed complete aneurysm exclusion, and the PCA was permeated and filled the PCA territory. Clinical follow-up at 14 months showed the patient with no deficits and a return to normal life.CONCLUSION: To our knowledge, this is the first report of a giant fusiform aneurysm of the PCA associated with P1-P2 segment fenestration and other variations of the basilar apex (bilateral superior cerebellar artery duplication and caudal fusion). Comprehension of the embryology and anatomy of the PCA and its related vessels and branches is fundamental to the decision-making process for a PCA aneurysm, especially when parent vessel occlusion is planned.

Cryptic sexual populations account for genetic diversity and ecological success in a widely distributed, asexual fungus-growing ant

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Activity pattern of Cuniculus paca (Rodentia: Cuniculidae) in relation to lunar illumination and other abiotic variables in the southern Brazilian Amazon

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Microhabitat selection and daily movements of two rodents (Necromys lasiurus and Oryzomys scotti) in Brazilian Cerrado, as revealed by a spool-and-line device

Studies on patterns of habitat use by mammals are necessary for understanding the mechanisms involved in their distribution and abundance. In this study, we used the spool-and-line method to investigate habitat utilization by two sigmodontine rodents from Brazilian Cerrado, Necromys lasiurus and Oryzomys scotti. We conducted the study in a Cerrado area in central Brazil (15 degrees 56'S and e 47 degrees 56'W) where the animals were caught in an area of 7.68 ha of Cerrado sensu stricto. Captured individuals were marked, equipped with a spool-and-Line device, and released at the same capture point. The next day we followed the thread to record their daily movements and find their nests. To investigate microhabitat selection we compared habitat characteristics along traits of each studied species with general habitat characteristics of the study area. Although the mean 24-h distance was greater for N. lasiurus (mean +/- SE: 41.9 +/- 42.2 m, N=3) than for O. scotti (28.7 +/- 14.2 m, N=6) this difference was not significant (Mann-Whitney test, U=26, P>0.6). We detected significant differences among observed microhabitats variables of both species and available microhabitat characteristics as determined by discriminant analysis (Wilks's lambda F=3.001; df=14, 116; P<0.001). Both species were associated to microhabitat characteristics whose values differed markedly from the overall available habitat. Along the first canonical discriminant function of the DFA both them were associated with greater grass height than the mean height available and along the second axis N. lasiurus selected areas with higher fruit availability and more shelters than those selected by 0. scotti. For stronger inferences regarding differential patterns of habitat utilization by Cerrado rodents we suggest the simultaneous use of both spool-and-line and standard trapping methods. (c) 2005 Deutsche Geseltschaft fur Saugetierkunde. Published by Elsevier GmbH. ALL rights reserved.

Nebular gas drag and co-orbital system dynamics

Aims. We study trajectories of planetesimals whose orbits decay due to gas drag in a primordial solar nebula and are perturbed by the gravity of the secondary body on an eccentric orbit whose mass ratio takes values from mu(2) = 10(-7) to mu(2) = 10(-3) increasing ten times at each step. Each planetesimal ultimately suffers one of the three possible fates: (1) trapping in a mean motion resonance with the secondary body; (2) collision with the secondary body and consequent increase of its mass; or (3) diffusion after crossing the orbit of the secondary body.Methods. We take the Burlirsh-Stoer numerical algorithm in order to integrate the Newtonian equations of the planar, elliptical restricted three-body problem with the secondary body and the planetesimal orbiting the primary. It is assumed that there is no interaction among planetesimals, and also that the gas does not affect the orbit of the secondary body.Results. The results show that the optimal value of the gas drag constant k for the 1: 1 resonance is between 0.9 and 1.25, representing a meter size planetesimal for each AU of orbital radius. In this study, the conditions of the gas drag are such that in theory, L4 no longer exists in the circular case for a critical value of k that defines a limit size of the planetesimal, but for a secondary body with an eccentricity larger than 0.05 when mu(2) = 10(-6), it reappears. The decrease of the cutoff collision radius increase the difusions but does not affect the distribution of trapping. The contribution to the mass accretion of the secondary body is over 40% with a collision radius 0.05R(Hill) and less than 15% with 0.005R(Hill) for mu(2) = 10(-7). The trappings no longer occur when the drag constant k reachs 30. That means that the size limit of planetesimal trapping is 0.2 m per AU of orbital radius. In most cases, this accretion occurs for a weak gas drag and small secondary eccentricity. The diffusions represent most of the simulations showing that gas drag is an efficient process in scattering planetesimals and that the trapping of planetesimals in the 1: 1 resonance is a less probable fate. These results depend on the specific drag force chosen.