Axial ligand influence on geometries, charge distributions and electronic structures of iron tetraazamacrocycle [Fe((II))TIM(X)(Y)](2+) complexes assessed by Density Functional Theory

We employed the Density Functional Theory along with small basis sets, B3LYP/LANL2DZ, for the study of FeTIM complexes with different pairs of axial ligands (CO, H(2)O, NH(3), imidazole and CH(3)CN). These calculations did not result in relevant changes of molecular quantities as bond lengths, vibrational frequencies and electronic populations supporting any significant back-donation to the carbonyl or acetonitrile axial ligands. Moreover, a back-donation mechanism to the macrocycle cannot be used to explain the observed changes in molecular properties along these complexes with CO or CH(3)CN. This work also indicates that complexes with CO show smaller binding energies and are less stable than complexes with CH(3)CN. Further, the electronic band with the largest intensity in the visible region (or close to this region) is associated to the transition from an occupied 3d orbital on iron to an empty pi* orbital located at the macrocycle. The energy of this Metal-to-Ligand Charge Transfer (MLCT) transition shows a linear relation to the total charge of the macrocycle in these complexes as given by Mulliken or Natural Population Analysis (NPA) formalisms. Finally, the macrocycle total charge seems to be influenced by the field induced by the axial ligands. (C) 2011 Elsevier Ltd. All rights reserved.

Does road network density matter in optimally locating facilities?

Optimal location on the transport infrastructure is the preferable requirement for many decision making processes. Most studies have focused on evaluating performances of optimally locate p facilities by minimizing their distances to a geographically distributed demand (n) when p and n vary. The optimal locations are also sensitive to geographical context such as road network, especially when they are asymmetrically distributed in the plane. The influence of alternating road network density is however not a very well-studied problem especially when it is applied in a real world context. This paper aims to investigate how the density level of the road network affects finding optimal location by solving the specific case of p-median location problem. A denser network is found needed when a higher number of facilities are to locate. The best solution will not always be obtained in the most detailed network but in a middle density level. The solutions do not further improve or improve insignificantly as the density exceeds 12,000 nodes, some solutions even deteriorate. The hierarchy of the different densities of network can be used according to location and transportation purposes and increase the efficiency of heuristic methods. The method in this study can be applied to other location-allocation problem in transportation analysis where the road network density can be differentiated. 

PokerMapper: : mapping executive functions, poker playing ability and responsible gambling in online environments

Research objectives Poker and responsible gambling both entail the use of the executive functions (EF), which are higher-level cognitive abilities. The main objective of this work was to assess if online poker players of different ability show different performances in their EF and if so, which functions are the most discriminating ones. The secondary objective was to assess if the EF performance can predict the quality of gambling, according to the Gambling Related Cognition Scale (GRCS), the South Oaks Gambling Screen (SOGS) and the Problem Gambling Severity Index (PGSI). Sample and methods The study design consisted of two stages: 46 Italian active players (41m, 5f; age 32±7,1ys; education 14,8±3ys) fulfilled the PGSI in a secure IT web system and uploaded their own hand history files, which were anonymized and then evaluated by two poker experts. 36 of these players (31m, 5f; age 33±7,3ys; education 15±3ys) accepted to take part in the second stage: the administration of an extensive neuropsychological test battery by a blinded trained professional. To answer the main research question we collected all final and intermediate scores of the EF tests on each player together with the scoring on the playing ability. To answer the secondary research question, we referred to GRCS, PGSI and SOGS scores.  We determined which variables that are good predictors of the playing ability score using statistical techniques able to deal with many regressors and few observations (LASSO, best subset algorithms and CART). In this context information criteria and cross-validation errors play a key role for the selection of the relevant regressors, while significance testing and goodness-of-fit measures can lead to wrong conclusions.   Preliminary findings We found significant predictors of the poker ability score in various tests. In particular, there are good predictors 1) in some Wisconsin Card Sorting Test items that measure flexibility in choosing strategy of problem-solving, strategic planning, modulating impulsive responding, goal setting and self-monitoring, 2) in those Cognitive Estimates Test variables related to deductive reasoning, problem solving, development of an appropriate strategy and self-monitoring, 3) in the Emotional Quotient Inventory Short (EQ-i:S) Stress Management score, composed by the Stress Tolerance and Impulse Control scores, and in the Interpersonal score (Empathy, Social Responsibility, Interpersonal Relationship). As for the quality of gambling, some EQ-i:S scales scores provide the best predictors: General Mood for the PGSI; Intrapersonal (Self-Regard; Emotional Self-Awareness, Assertiveness, Independence, Self-Actualization) and Adaptability  (Reality Testing, Flexibility, Problem Solving) for the SOGS, Adaptability for the GRCS. Implications for the field Through PokerMapper we gathered knowledge and evaluated the feasibility of the construction of short tasks/card games in online poker environments for profiling users’ executive functions. These card games will be part of an IT system able to dynamically profile EF and provide players with a feedback on their expected performance and ability to gamble responsibly in that particular moment. The implementation of such system in existing gambling platforms could lead to an effective proactive tool for supporting responsible gambling. 

Myth and Society: Functions, Uses, and Abuses of Myth in Society

In this work, I will discuss the integral role that myth has in society and then, after presenting several examples of this thesis, I will examine how the integral nature of myth lends itself to certain societal abuses. These abuses often result in unjust social constructs that eventually become attributed to the myth. I would like to proceed in defense of myth; that is, that these constructs are not to be attributed to the myths themselves, rather, society has taken myth and applied it to suit its purposes, ignoring the context in which the myths originated. Hopefully this will raise society's current attitudes toward myth to a level of respect, and will also help to clear myth of its reputation as the origin of injustice and domination.

Profile of cortisol, glycaemia, and blood parameters of American Bullfrog tadpoles Lithobates catesbeianus exposed to density and hypoxia stressors

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

Soybean compressibility and bulk density

The objective of this project was to study the influence of surcharge pressure and moisture content on the compressive behavior and bulk density of soybeans. Three varieties were selected with varying dimensions and shapes. Moisture contents of 10.5, 15.0, and 20% were tested at nine surcharge pressures in the range from 0 to 82.8 kPa. Results indicated that the bulk densities of different soybean varieties have similar behavior with respect to pressure level and moisture content but that the magnitude of bulk density was influenced by variety, Bulk density was influenced by both pressure level and moisture content. The four-element Burger model was found to adequately describe the bulk density of soybeans as a function of pressure for all varieties and moisture levels.

Effect of dietary energy and stocking density on the performance and sensible heat loss of broilers reared under tropical winter conditions

The objective of the present study was to evaluate the effects of different dietary energy levels and stocking densities on the thermoregulating parameters, live performance, and carcass traits of broilers reared under tropical winter conditions at different times of the day. In total, 1,312 one-d-old male broilers were used. Birds were allotted to three different stocking densities (10, 14 or 18 birds/m²) and two dietary energy levels (2900 or 3200 kcal ME/kg). The following parameters were evaluated:radiant heat load (RHL), rectal temperature (RT), feed intake (FI), weight gain (WG), feed conversion ratio (FCR), livability (L), production of live weight per area (WA), and carcass yield. Stocking density did not affect sensible heat loss (SRL) or rectal temperature (RT); however, as expected, sensible heat loss (SRL) and RT were influenced by time of the day, with higher values in the morning and in the afternoon, respectively. There was no effect of treatment (p>0.05) on carcass or parts yield. Feed intake was reduced in 3%, whereas weight gain and feed conversion ratio improved in 8 and 10%, respectively, as dietary energy level increased. on the other hand, stocking density did not influence live performance or carcass traits. Based on the present results, it is concluded that sensible heat loss depends on dietary energy levels and particularly on time of the day. Therefore, environmental house management is suggested during tropical winters in order to reduce differences between broiler skin and environmental temperatures in the morning and in the afternoon.

Determining the interfacial density of states in metal-insulator-semiconductor devices based on poly(3-hexylthiophene)

Low frequency admittance measurements are used to determine the density of interface states in metal-insulator-semiconductor diodes based on the unintentionally doped, p-type semiconductor poly(3-hexylthiophene). After vacuum annealing at 90 degrees C, interface hole trapping states are shown to be distributed in energy with their density decreasing approximately linearly from similar to 20x10(10) to 5x10(10) cm(-2) eV(-1) over an energy range extending from 0.05 to 0.25 eV above the bulk Fermi level. (c) 2008 American Institute of Physics.

Increased pancreatic islet mass is accompanied by activation of the insulin receptor substrate-2/serine-threonine kinase pathway and augmented cyclin D(2) protein levels in insulin-resistant rats

It is well known that glucocorticoids induce peripheral insulin resistance in rodents and humans. Here, we investigated the structural and ultrastructural modifications, as well as the proteins involved in beta-cell function and proliferation, in islets from insulin-resistant rats. Adult male Wistar rats were made insulin resistant by daily administration of dexamethasone (DEX; 1mg/kg, i.p.) for five consecutive days, whilst control (CTL) rats received saline alone. Structure analyses showed a marked hypertrophy of DEX islets with an increase of 1.7-fold in islet mass and of 1.6-fold in islet density compared with CTL islets (P < 0.05). Ultrastructural evaluation of islets revealed an increased amount of secreting organelles, such as endoplasmic reticulum and Golgi apparatus in DEX islets. Mitotic figures were observed in DEX islets at structural and ultrastructural levels. Beta-cell proliferation, evaluated at the immunohistochemical level using anti-PCNA (proliferating cell nuclear antigen), showed an increase in pancreatic beta-cell proliferation of 6.4-fold in DEX islets compared with CTL islets (P < 0.0001). Increases in insulin receptor substrate-2 (IRS-2), phosphorylated-serine-threonine kinase AKT (p-AKT), cyclin D(2) and a decrease in retinoblastoma protein (pRb) levels were observed in DEX islets compared with CTL islets (P < 0.05). Therefore, during the development of insulin resistance, the endocrine pancreas adapts itself increasing beta-cell mass and proliferation, resulting in an amelioration of the functions. The potential mechanisms that underlie these events involve the activation of the IRS-2/AKT pathway and activation of the cell cycle, mediated by cyclin D(2). These adaptations permit the maintenance of glycaemia at near-physiological ranges.

Incommensurate spin-density-wave and metal-insulator transition in the one-dimensional periodic Anderson model

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

Estudo da adsorção de hidrogênio e sulfeto na superfície de paládio: aspectos experimentais (eletroquímica) e teóricos (ab initio e Teoria do Funcional da Densidade)

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

Evaluation of TNF-alpha, IL-4, and IL-10 and parasite density in spleen and liver of L. (L.) chagasi naturally infected dogs

Dogs are the main domestic reservoirs of L. (L.) chagasi. Once in the vertebrate host, the parasite can cause visceral leishmaniasis, which can also be transmitted to humans. Cytokines are key elements of the host immune response against Leishmania spp. To investigate whether tumor necrosis factor (TNF)-alpha, interleukin (IL)-4 and IL-10 are associated with pattern infection in dogs, these cytokines were quantified in the spleen and liver of dogs naturally infected with L. (L.) chagasi, with or without clinical manifestations, and their levels were correlated with the parasite load verified in these organs. A total of 40 adult dogs naturally infected with L. (L.) chagasi were assessed, together with 12 uninfected control dogs. Samples from spleen and liver were used to determine the cytokine levels by capture ELISA and for quantifying parasite load by real-time PCR. Statistical analysis was performed using the minimum Chi square method and group means were compared using the Tukey test. TNF-alpha, IL-4 and IL-10 levels in infected dogs were higher than in control groups; the liver was the main cytokine-producing organ during infection. The level of splenic TNF-alpha showed correlation with parasite load and may represent an important marker for infection process evolution, with the participation of IL-10. These results may contribute to a clearer understanding of the immune response in dogs infected with L. (L.) chagasi, which may lead to the development of prophylactic or preventive measures for these animals.

Therapeutic Effects of Low-Level Laser Therapy After Premolar Extraction in Adolescents: A Randomized Double-Blind Clinical Trial

Objective: The purpose of this study was to evaluate the effect of low-level laser therapy (LLLT) on wound healing process and pain levels after premolar extraction in adolescents. Background data: The advantage of using LLLT in oral surgeries is the reduction of inflammation and postoperative discomfort; however, the optimal dosing parameters and treatment effects in surgical procedures are inconclusive. Methods: A double-blind, randomized, controlled clinical trial was conducted with 14 patients who were to undergo surgical removal of premolars. Patients were randomly allocated to the LLLT (test) group and placebo (control) group. Patients in the test group received 5.1 J (60 J/cm(2)) of energy density of a gallium-aluminum-arsenide (GaAlAs) diode laser (wavelength, 830 nm; output power, 0.1 W) at three different points intraorally, 1 cm from the target tissue immediately and at 48 and 72 h after the surgical procedure. For patients in the placebo group, the laser device was applied to the same points without activating the hand piece. The wound healing process was evaluated by an independent examiner by visual inspection with the support of digital photographs at baseline and 2, 7, and 15 days postoperatively. Patients recorded the degree of pain using the visual analogue scale (VAS). Results: Compared with the placebo group, the test group showed a lower intensity of pain, but this difference was not statistically significant at any time point. The wound healing process was similar in both groups. Conclusions: Within the limitations of this study, the LLLT parameters used neither increased the wound healing process nor significantly decreased pain intensity after premolar extraction in adolescents.

Radiographic assessment of bone density around integrated titanium implants after ovariectomy in rats

Objectives:This study evaluated the influence of ovariectomy 8 weeks after implant placement on bone integrated to titanium implants.Materials and methods:Thirty-eight female rats were submitted to a titanium implant at the tibiae proximal methaphysis. After a healing period of 8 weeks the animals were randomly divided into three groups: control (CTL-10 animals), sham-operated (SHAM-14 animals) and ovariectomy (OVX-14 animals). The CTL group was then sacrificed in order to confirm integration of the implant. The SHAM group was submitted to fictitious surgery and the OVX group was submitted to bilateral ovariectomy. After 12 weeks post-implant placement, the SHAM and OVX groups were sacrificed. In order to confirm the systemic osteopenia in rats, a dual-energy X-ray absorptiometry (DXA) was performed. For the evaluation of bone density, digital radiographs were taken. The grey level of the bone adjacent to implant was measured using image software and the bone density was calculated at six points on both sides of the implant.Results:Densitometry measurements of the femur confirmed systemic bone mass loss in the OVX group. Individualized bone analyses of different regions surrounding the implant showed a significantly lower radiographic bone density (P < 0.05) in the cancellous region of the OVX group (77.48 +/- 23.39 grey levels) when compared with the CTL and SHAM groups (91.61 +/- 32.10 and 102.57 +/- 32.50 grey levels, respectively).Conclusions:The present study showed a decrease of the radiographic bone density in the cancellous region of bone around titanium implants placed 8 weeks before ovariectomy in rats.

Influence of homeopathic treatment with comfrey on bone density around titanium implants. A digital subtraction radiography study in rats

Objective: The objective of this study was to evaluate the influence of homeopathic treatment with comfrey (Shymphytum officinalis 6CH) on radiographic bone density and area around titanium implants.Material and methods: Forty-eight rats were divided into two groups of 24 animals each: a control group (C) and a test group (SO). Each animal received one titanium micro-implant placed in the tibia. The animals in Group SO were subjected to 10 drops of comfrey 6CH per day mixed into their drinking water until the day of sacrifice. Eight animals of each group were sacrificed at 7, 14 and 28 days post-surgery, respectively.Standardized digital radiographs were obtained on the day of implant installation (baseline images) and on the day of sacrifice (final images). Digital subtraction of the two corresponding images was performed to evaluate changes in bone density and the area related to change around the implant between baseline and final images.Results: Subtraction images demonstrated that a significant difference existed in mean shade of gray at 14 days post-surgery between Group SO (mean 175.3 +/- 14.4) and Group C (mean 146.2 +/- 5.2). Regarding the area in pixels corresponding to the bone gain in Group SO, the differences observed between the sacrifice periods and groups were only significant at 7 days sacrifice between Group SO (mean 171.2 +/- 21.9) and Group C (mean 64.5 +/- 60.4).Conclusion: Within the limits of this study, comfrey administration promotes an increase in radiographic bone density around titanium implants in the initial period of bone healing.