Electronic And Structural Study Of Pt-modified Au Vicinal Surfaces: A Model System For Pt-au Catalysts.

Two single crystalline surfaces of Au vicinal to the (111) plane were modified with Pt and studied using scanning tunneling microscopy (STM) and X-ray photoemission spectroscopy (XPS) in ultra-high vacuum environment. The vicinal surfaces studied are Au(332) and Au(887) and different Pt coverage (θPt) were deposited on each surface. From STM images we determine that Pt deposits on both surfaces as nanoislands with heights ranging from 1 ML to 3 ML depending on θPt. On both surfaces the early growth of Pt ad-islands occurs at the lower part of the step edge, with Pt ad-atoms being incorporated into the steps in some cases. XPS results indicate that partial alloying of Pt occurs at the interface at room temperature and at all coverage, as suggested by the negative chemical shift of Pt 4f core line, indicating an upward shift of the d-band center of the alloyed Pt. Also, the existence of a segregated Pt phase especially at higher coverage is detected by XPS. Sample annealing indicates that the temperature rise promotes a further incorporation of Pt atoms into the Au substrate as supported by STM and XPS results. Additionally, the catalytic activity of different PtAu systems reported in the literature for some electrochemical reactions is discussed considering our findings.

Discovery Of A Rare Pterosaur Bone Bed In A Cretaceous Desert With Insights On Ontogeny And Behavior Of Flying Reptiles.

A pterosaur bone bed with at least 47 individuals (wing spans: 0.65-2.35 m) of a new species is reported from southern Brazil from an interdunal lake deposit of a Cretaceous desert, shedding new light on several biological aspects of those flying reptiles. The material represents a new pterosaur, Caiuajara dobruskii gen. et sp. nov., that is the southermost occurrence of the edentulous clade Tapejaridae (Tapejarinae, Pterodactyloidea) recovered so far. Caiuajara dobruskii differs from all other members of this clade in several cranial features, including the presence of a ventral sagittal bony expansion projected inside the nasoantorbital fenestra, which is formed by the premaxillae; and features of the lower jaw, like a marked rounded depression in the occlusal concavity of the dentary. Ontogenetic variation of Caiuajara dobruskii is mainly reflected in the size and inclination of the premaxillary crest, changing from small and inclined (∼ 115°) in juveniles to large and steep (∼ 90°) in adults. No particular ontogenetic features are observed in postcranial elements. The available information suggests that this species was gregarious, living in colonies, and most likely precocial, being able to fly at a very young age, which might have been a general trend for at least derived pterosaurs.

Behavior Of Listeria Monocytogenes In A Multi-species Biofilm With Enterococcus Faecalis And Enterococcus Faecium And Control Through Sanitation Procedures.

The formation of mono-species biofilm (Listeria monocytogenes) and multi-species biofilms (Enterococcus faecium, Enterococcus faecalis, and L. monocytogenes) was evaluated. In addition, the effectiveness of sanitation procedures for the control of the multi-species biofilm also was evaluated. The biofilms were grown on stainless steel coupons at various incubation temperatures (7, 25 and 39°C) and contact times (0, 1, 2, 4, 6 and 8days). In all tests, at 7°C, the microbial counts were below 0.4 log CFU/cm(2) and not characteristic of biofilms. In mono-species biofilm, the counts of L. monocytogenes after 8days of contact were 4.1 and 2.8 log CFU/cm(2) at 25 and 39°C, respectively. In the multi-species biofilms, Enterococcus spp. were present at counts of 8 log CFU/cm(2) at 25 and 39°C after 8days of contact. However, the L. monocytogenes in multi-species biofilms was significantly affected by the presence of Enterococcus spp. and by temperature. At 25°C, the growth of L. monocytogenes biofilms was favored in multi-species cultures, with counts above 6 log CFU/cm(2) after 8days of contact. In contrast, at 39°C, a negative effect was observed for L. monocytogenes biofilm growth in mixed cultures, with a significant reduction in counts over time and values below 0.4 log CFU/cm(2) starting at day 4. Anionic tensioactive cleaning complemented with another procedure (acid cleaning, disinfection or acid cleaning+disinfection) eliminated the multi-species biofilms under all conditions tested (counts of all micro-organisms<0.4 log CFU/cm(2)). Peracetic acid was the most effective disinfectant, eliminating the multi-species biofilms under all tested conditions (counts of the all microorganisms <0.4 log CFU/cm(2)). In contrast, biguanide was the least effective disinfectant, failing to eliminate biofilms under all the test conditions.

Biofilm And Saliva Affect The Biomechanical Behavior Of Dental Implants.

Friction coefficient (FC) was quantified between titanium-titanium (Ti-Ti) and titanium-zirconia (Ti-Zr), materials commonly used as abutment and implants, in the presence of a multispecies biofilm (Bf) or salivary pellicle (Pel). Furthermore, FC was used as a parameter to evaluate the biomechanical behavior of a single implant-supported restoration. Interface between Ti-Ti and Ti-Zr without Pel or Bf was used as control (Ctrl). FC was recorded using tribometer and analyzed by two-way Anova and Tukey test (p<0.05). Data were transposed to a finite element model of a dental implant-supported restoration. Models were obtained varying abutment material (Ti and Zr) and FCs recorded (Bf, Pel, and Ctrl). Maximum and shear stress were calculated for bone and equivalent von Misses for prosthetic components. Data were analyzed using two-way ANOVA (p<0.05) and percentage of contribution for each condition (material and FC) was calculated. FC significant differences were observed between Ti-Ti and Ti-Zr for Ctrl and Bf groups, with lower values for Ti-Zr (p<0.05). Within each material group, Ti-Ti differed between all treatments (p<0.05) and for Ti-Zr, only Pel showed higher values compared with Ctrl and Bf (p<0.05). FC contributed to 89.83% (p<0.05) of the stress in the screw, decreasing the stress when the FC was lower. FC resulted in an increase of 59.78% of maximum stress in cortical bone (p=0.05). It can be concluded that the shift of the FC due to the presence of Pel or Bf is able to jeopardize the biomechanical behavior of a single implant-supported restoration.

Key Participants Of The Tumor Microenvironment Of The Prostate: An Approach Of The Structural Dynamic Of Cellular Elements And Extracellular Matrix Components During Epithelial-stromal Transition.

Cancer is a multistep process that begins with the transformation of normal epithelial cells and continues with tumor growth, stromal invasion and metastasis. The remodeling of the peritumoral environment is decisive for the onset of tumor invasiveness. This event is dependent on epithelial-stromal interactions, degradation of extracellular matrix components and reorganization of fibrillar components. Our research group has studied in a new proposed rodent model the participation of cellular and molecular components in the prostate microenvironment that contributes to cancer progression. Our group adopted the gerbil Meriones unguiculatus as an alternative experimental model for prostate cancer study. This model has presented significant responses to hormonal treatments and to development of spontaneous and induced neoplasias. The data obtained indicate reorganization of type I collagen fibers and reticular fibers, synthesis of new components such as tenascin and proteoglycans, degradation of basement membrane components and elastic fibers and increased expression of metalloproteinases. Fibroblasts that border the region, apparently participate in the stromal reaction. The roles of each of these events, as well as some signaling molecules, participants of neoplastic progression and factors that promote genetic reprogramming during epithelial-stromal transition are also discussed.

Structural aspects of the p.P222Q homozygous mutation of HSD3B2 gene in a patient with congenital adrenal hyperplasia

Type II 3β-hydroxysteroid dehydrogenase/Δ5-Δ4-isomerase (3β-HSD2), encoded by the HSD3B2 gene, is a key enzyme involved in the biosynthesis of all the classes of steroid hormones. Deleterious mutations in the HSD3B2 gene cause the classical deficiency of 3β-HSD2, which is a rare autosomal recessive disease that leads to congenital adrenal hyperplasia (CAH). CAH is the most frequent cause of ambiguous genitalia and adrenal insufficiency in newborn infants with variable degrees of salt losing. Here we report the molecular and structural analysis of the HSD3B2 gene in a 46,XY child, who was born from consanguineous parents, and presented with ambiguous genitalia and salt losing. The patient carries a homozygous nucleotide c.665C>A change in exon 4 that putatively substitutes the proline at codon 222 for glutamine. Molecular homology modeling of normal and mutant 3β-HSD2 enzymes emphasizes codon 222 as an important residue for the folding pattern of the enzyme and validates a suitable model for analysis of new mutations.

Structural properties of lipid reconstructs and lipid composition of normotensive and hypertensive rat vascular smooth muscle cell membranes

Multiple cell membrane alterations have been reported to be the cause of various forms of hypertension. The present study focuses on the lipid portion of the membranes, characterizing the microviscosity of membranes reconstituted with lipids extracted from the aorta and mesenteric arteries of spontaneously hypertensive (SHR) and normotensive control rat strains (WKY and NWR). Membrane-incorporated phospholipid spin labels were used to monitor the bilayer structure at different depths. The packing of lipids extracted from both aorta and mesenteric arteries of normotensive and hypertensive rats was similar. Lipid extract analysis showed similar phospholipid composition for all membranes. However, cholesterol content was lower in SHR arteries than in normotensive animal arteries. These findings contrast with the fact that the SHR aorta is hyporeactive while the SHR mesenteric artery is hyperreactive to vasopressor agents when compared to the vessels of normotensive animal strains. Hence, factors other than microviscosity of bulk lipids contribute to the vascular smooth muscle reactivity and hypertension of SHR. The excess cholesterol in the arteries of normotensive animal strains apparently is not dissolved in bulk lipids and is not directly related to vascular reactivity since it is present in both the aorta and mesenteric arteries. The lower cholesterol concentrations in SHR arteries may in fact result from metabolic differences due to the hypertensive state or to genes that co-segregate with those that determine hypertension during the process of strain selection.

Electrochemical behavior of parent and photodegradation products of some selected pesticides

Electrochemical behavior of pesticides is extensively studied, but little attention has been given to the study of their degradation products (by-products) by electrochemical methods. However, the degradation products of pesticides can be even more toxic then the parent products and such studies should be encouraged. Therefore, the objective of this work was to evaluate the electroactivity of by-products of imazaquin, methylparathion, bentazon and atrazine, generated by UV irradiation and measured using cyclic and differential pulse voltammetry and UV-visible absorption spectrophotometry. Results have shown that several by-products exhibit electroactivity, allowing, in some cases, the simultaneous determination of both parent and degradation products.

Synthesis and structural characterization of block and random low molecular weight copolymers composed of L-lactic acid and isosorbide succinate moieties

Isosorbide succinate moieties were incorporated into poly(L-lactide) (PLLA) backbone in order to obtain a new class of biodegradable polymer with enhanced properties. This paper describes the synthesis and characterization of four types of low molecular weight copolymers. Copolymer I was obtained from monomer mixtures of L-lactide, isosorbide, and succinic anhydride; II from oligo(L-lactide) (PLLA), isosorbide, and succinic anhydride; III from oligo(isosorbide succinate) (PIS) and L-lactide; and IV from transesterification reactions between PLLA and PIS. MALDI-TOFMS and 13C-NMR analyses gave evidence that co-oligomerization was successfully attained in all cases. The data suggested that the product I is a random co-oligomer and the products II-IV are block co-oligomers.

Herbage accumulation, growth and structural characteristics of Mombasa grass (Panicum maximum Jacq.) harvested at different cutting intervals

The objective of the present study was to evaluate herbage accumulation, morphological composition, growth rate and structural characteristics in Mombasa grass swards subject to different cutting intervals (3, 5 and 7 wk) during the rainy and dry seasons of the year. Treatments were assigned to experimental units (17.5 m(2)) according to a complete randomised block design, with four replicates. Herbage accumulation was greater in the rainy than in the dry season (83 and 17%, respectively). Herbage accumulation (24,300 kg DM ha(-1)), average growth rate (140 kg DM ha(-1) d(-1)) and sward height (111 cm) were highest in the 7 wk cutting interval, but leaf proportion (56%), leaf:stem (1.6) and leaf:non leaf (1.3) ratios decreased. Herbage accumulation, morphological composition and sward structure of Mombasa grass sward may be manipulated through defoliation frequency. The highest leaf proportion was recorded in the 3-wk cutting interval. Longer cutting intervals affected negatively sward structure, with potential negative effects on utilization efficiency, animal intake and performance.

Interaction and behavior of virgin and physogastric queens in three Meliponini species (Hymenoptera, Apidae)

We studied the behavior of virgin queens of the stingless bee species Schwarziana quadripunctata, Paratrigona lineata and Tetragona clavipes, investigating internal nest activities, including the cell provisioning and oviposition process. We made direct observation of queen behavior, with the aid of video filming. Forty-four virgin queens of S. quadripunctata were observed; one was larger and more attractive than the others. Miniature queens were more abundant than normal-size queens; both were found in prison chambers. Agonistic behavior between virgin and physogastric queens of P. lineata was observed during attempts at queen supersedure. After the disappearance of the physogastric queen and the appearance of a virgin queen in T. clavipes nests, the brood cells were sealed with pollen alone, but no egg. In all three species, the presence of one or more virgin queens appeared to make the colonies nervous, even though constant production of virgin queens is vital to the survival of the colony and is part of the colony cycle in these bees.

Comparative study of the hygienic behavior of Carniolan and Africanized honey bees directed towards grouped versus isolated dead brood cells

In Apis mellifera, hygienic behavior involves recognition and removal of sick, damaged or dead brood from capped cells. We investigated whether bees react in the same way to grouped versus isolated damaged capped brood cells. Three colonies of wild-type Africanized honey bees and three colonies of Carniolan honey bees were used for this investigation. Capped worker brood cells aged 12 to 14 days old were perforated with the pin-killing method. After making holes in the brood cells, the combs were placed back into the hives; 24 h later the number of cleaned cells was recorded in areas with pin-killed and control brood cells. Four repetitions were made in each colony. Isolated cells were more frequently cleaned than grouped cells, though variance analysis showed no significant difference (P = 0.1421). Carniolan bees also were somewhat, though not significantly more hygienic than Africanized honey bees (P = 0.0840). We conclude that honey bees can detect and remove both isolated and grouped dead brood. The tendency towards greater hygienic efficiency directed towards grouped pin-killed brood may be a consequence of a greater concentration of volatiles emanating from the wounds in the dead pupae.

Structural basis of GC-1 selectivity for thyroid hormone receptor isoforms

Background: Thyroid receptors, TRa and TR beta, are involved in important physiological functions such as metabolism, cholesterol level and heart activities. Whereas metabolism increase and cholesterol level lowering could be achieved by TR beta isoform activation, TRa activation affects heart rates. Therefore, beta-selective thyromimetics have been developed as promising drug-candidates for treatment of obesity and elevated cholesterol level. GC-1 [ 3,5-dimethyl-4-(4'-hydroxy- 3'-isopropylbenzyl)-phenoxy acetic acid] has ability to lower LDL cholesterol with 600-to 1400-fold more potency and approximately two-to threefold more efficacy than atorvastatin (Lipitor(C)) in studies in rats, mice and monkeys. Results: To investigate GC-1 specificity, we solved crystal structures and performed molecular dynamics simulations of both isoforms complexed with GC-1. Crystal structures reveal that, in TRa Arg228 is observed in multiple conformations, an effect triggered by the differences in the interactions between GC-1 and Ser277 or the corresponding asparagine (Asn331) of TR beta. The corresponding Arg282 of TR beta is observed in only one single stable conformation, interacting effectively with the ligand. Molecular dynamics support this model: our simulations show that the multiple conformations can be observed for the Arg228 in TR alpha, in which the ligand interacts either strongly with the ligand or with the Ser277 residue. In contrast, a single stable Arg282 conformation is observed for TR beta, in which it strongly interacts with both GC-1 and the Asn331. Conclusion: Our analysis suggests that the key factors for GC-1 selectivity are the presence of an oxyacetic acid ester oxygen and the absence of the amino group relative to T(3). These results shed light into the beta-selectivity of GC-1 and may assist the development of new compounds with potential as drug candidates to the treatment of hypercholesterolemia and obesity.

Hygienic behavior of the stingless bee Plebeia remota (Holmberg, 1903) (Apidae, Meliponini)

We investigated hygienic behavior in 10 colonies of Plebeia remota, using the pin-killed method. After 24 h the bees had removed a mean of 69.6% of the dead brood. After 48 h, the bees had removed a mean of 96.4% of the dead brood. No significant correlation was found between the size of the brood comb and the number of dead pupae removed, and there was no apparent effect of the origin and the condition of the colony on the hygienic behavior of the bees. Plebeia remota has an efficiency of hygienic behavior superior to that of three of the other four stingless bee species studied until now.

Magnetic behavior of 10 nm-magnetite particles diluted in lyotropic liquid crystals

A magnetic study of 10 nm magnetite nanoparticles diluted in lyotropic liquid crystal and common liquids was carried out. In the liquid crystal the ZFC-FC curves showed a clear irreversible behavior, and it was possible to distinguish the nematic from the isotropic phase since the magnetization followed the dependence of the nematic order parameter with the temperature. This behavior could be mimicked by Monte Carlo simulation. (C) 2011 American Institute of Physics. [doi:10.1063/1.3549616]