Conformational analysis, stereoelectronic interactions and NMR properties of 2-fluorobicyclo[2.2.1]heptan-7-ols

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Four diastereoisomers of 2-fluorobicyclo[2.2.1]heptan-7-ols were computationally investigated by using quantum-chemical calculations, and their relative energies were analyzed on the basis of stereoelectronic interactions, particularly the presence or otherwise of the F center dot center dot center dot HO intramolecular hydrogen bond in the syn-exo isomer. It was found through NBO and AIM analyses that such an interaction contributes to structural stabilization and that the (1h)J(F),(H(O)) coupling constant in the syn-exo isomer is modulated by the n(F)->sigma*(OH) interaction, i.e., the quantum nature of the F center dot center dot center dot HO hydrogen bond.812271232Fundação de Amparo à Pesquisa do Estado de Minas Gerais (FAPEMIG)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq

Combined effects of time spent in physical activity, sedentary behaviors and sleep on obesity and cardio-metabolic health markers: a novel compositional data analysis approach

<div><p>The associations between time spent in sleep, sedentary behaviors (SB) and physical activity with health are usually studied without taking into account that time is finite during the day, so time spent in each of these behaviors are codependent. Therefore, little is known about the combined effect of time spent in sleep, SB and physical activity, that together constitute a composite whole, on obesity and cardio-metabolic health markers. Cross-sectional analysis of NHANES 2005–6 cycle on N = 1937 adults, was undertaken using a compositional analysis paradigm, which accounts for this intrinsic codependence. Time spent in SB, light intensity (LIPA) and moderate to vigorous activity (MVPA) was determined from accelerometry and combined with self-reported sleep time to obtain the 24 hour time budget composition. The distribution of time spent in sleep, SB, LIPA and MVPA is significantly associated with BMI, waist circumference, triglycerides, plasma glucose, plasma insulin (all p<0.001), and systolic (p<0.001) and diastolic blood pressure (p<0.003), but not HDL or LDL. Within the composition, the strongest positive effect is found for the proportion of time spent in MVPA. Strikingly, the effects of MVPA replacing another behavior and of MVPA being displaced by another behavior are asymmetric. For example, re-allocating 10 minutes of SB to MVPA was associated with a lower waist circumference by 0.001% but if 10 minutes of MVPA is displaced by SB this was associated with a 0.84% higher waist circumference. The proportion of time spent in LIPA and SB were detrimentally associated with obesity and cardiovascular disease markers, but the association with SB was stronger. For diabetes risk markers, replacing SB with LIPA was associated with more favorable outcomes. Time spent in MVPA is an important target for intervention and preventing transfer of time from LIPA to SB might lessen the negative effects of physical inactivity.</p></div

Modified spin-wave study of random antiferromagnetic-ferromagnetic spin chains

We study the thermodynamics of one-dimensional quantum spin-1/2 Heisenberg ferromagnetic system with random antiferromagnetic impurity bonds. In the dilute impurity limit, we generalize the modified spin-wave theory for random spin chains, where local chemical potentials for spin-waves in ferromagnetic spin segments are introduced to ensure zero magnetization at finite temperature. This approach successfully describes the crossover from behavior of pure one-dimensional ferromagnet at high temperatures to a distinct Curie behavior due to randomness at low temperatures. We discuss the effects of impurity bond strength and concentration on the crossover and low temperature behavior.Comment: 14 pages, 7 eps figure

Spatial Guilds in the Serengeti Food Web Revealed by a Bayesian Group Model

Food webs, networks of feeding relationships among organisms, provide fundamental insights into mechanisms that determine ecosystem stability and persistence. Despite long-standing interest in the compartmental structure of food webs, past network analyses of food webs have been constrained by a standard definition of compartments, or modules, that requires many links within compartments and few links between them. Empirical analyses have been further limited by low-resolution data for primary producers. In this paper, we present a Bayesian computational method for identifying group structure in food webs using a flexible definition of a group that can describe both functional roles and standard compartments. The Serengeti ecosystem provides an opportunity to examine structure in a newly compiled food web that includes species-level resolution among plants, allowing us to address whether groups in the food web correspond to tightly-connected compartments or functional groups, and whether network structure reflects spatial or trophic organization, or a combination of the two. We have compiled the major mammalian and plant components of the Serengeti food web from published literature, and we infer its group structure using our method. We find that network structure corresponds to spatially distinct plant groups coupled at higher trophic levels by groups of herbivores, which are in turn coupled by carnivore groups. Thus the group structure of the Serengeti web represents a mixture of trophic guild structure and spatial patterns, in contrast to the standard compartments typically identified in ecological networks. From data consisting only of nodes and links, the group structure that emerges supports recent ideas on spatial coupling and energy channels in ecosystems that have been proposed as important for persistence.Comment: 28 pages, 6 figures (+ 3 supporting), 2 tables (+ 4 supporting

Tricritical Points in the Sherrington-Kirkpatrick Model in the Presence of Discrete Random Fields

The infinite-range-interaction Ising spin glass is considered in the presence of an external random magnetic field following a trimodal (three-peak) distribution. The model is studied through the replica method and phase diagrams are obtained within the replica-symmetry approximation. It is shown that the border of the ferromagnetic phase may present first-order phase transitions, as well as tricritical points at finite temperatures. Analogous to what happens for the Ising ferromagnet under a trimodal random field, it is verified that the first-order phase transitions are directly related to the dilution in the fields (represented by $p_{0}$). The ferromagnetic boundary at zero temperature also exhibits an interesting behavior: for $0<p_{0}<p_{0}^{*} \approx 0.30856$, a single tricritical point occurs, whereas if $p_{0}>p_{0}^{*}$ the critical frontier is completely continuous; however, for $p_{0}=p_{0}^{*}$, a fourth-order critical point appears. The stability analysis of the replica-symmetric solution is performed and the regions of validity of such a solution are identified; in particular, the Almeida-Thouless line in the plane field versus temperature is shown to depend on the weight $p_{0}$.Comment: 23pages, 7 ps figure

Risk of surgical site infection in patients undergoing orthopedic surgery

This study aimed to identify risk factors associated with surgical site infections in orthopedic surgical patients at a public hospital in Minas Gerais, Brazil, between 2005 and 2007. A historical cohort of 3,543 patients submitted to orthopedic surgical procedures. A descriptive analysis was conducted and surgical site infection incidence rates were estimated. To verify the association between infection and risk factors, the Chi-square Test was used. The strength of association of the event with the independent variables was estimated using Relative Risk, with a 95% confidence interval and pEstudio para identificar factores de riesgo asociados a infecciones de sitio quirúrgico en pacientes quirúrgicos ortopédicos de un hospital público de Minas Gerais, Brasil, entre 2005 y 2007. Cohorte histórica de 3.543 pacientes sometidos a cirugías ortopédicas. Un análisis descriptivo fue realizado y la tasa de incidencia de infección fue estimada. Para verificar la asociación entre la infección y los factores de riesgo se usó el test chi-cuadrado. La fuerza de la asociación del evento con las variables independientes fue estimada por el Riesgo Relativo, con un intervalo de confianza de 95% y p Objetivou-se, neste estudo, identificar fatores de risco associados às infecções de sítio cirúrgico, em pacientes cirúrgicos ortopédicos, de um hospital público de Minas Gerais, Brasil, entre 2005 e 2007. Como método usou-se coorte histórica em 3.543 pacientes submetidos a cirurgias ortopédicas. Análise descritiva e taxa de incidência de infecção foram estimadas. Para verificar a associação entre a infecção e os fatores de risco usou-se o teste qui-quadrado. A força da associação do evento com as variáveis independentes foi estimada pelo risco relativo, intervalo de confiança de 95% e p<0,05. A incidência de infecção de sítio cirúrgico foi de 1,8%. Potencial de contaminação da ferida cirúrgica, condições clínicas do paciente, tempo cirúrgico e tipo de procedimento ortopédico foram estatisticamente associados à infecção. A identificação de associação de infecção de sítio cirúrgico aos fatores de risco mencionados é importante e contribui para a prática clínica do enfermeiro

Uncertainty-based Traffic Accident Anticipation with Spatio-Temporal Relational Learning

Traffic accident anticipation aims to predict accidents from dashcam videos as early as possible, which is critical to safety-guaranteed self-driving systems. With cluttered traffic scenes and limited visual cues, it is of great challenge to predict how long there will be an accident from early observed frames. Most existing approaches are developed to learn features of accident-relevant agents for accident anticipation, while ignoring the features of their spatial and temporal relations. Besides, current deterministic deep neural networks could be overconfident in false predictions, leading to high risk of traffic accidents caused by self-driving systems. In this paper, we propose an uncertainty-based accident anticipation model with spatio-temporal relational learning. It sequentially predicts the probability of traffic accident occurrence with dashcam videos. Specifically, we propose to take advantage of graph convolution and recurrent networks for relational feature learning, and leverage Bayesian neural networks to address the intrinsic variability of latent relational representations. The derived uncertainty-based ranking loss is found to significantly boost model performance by improving the quality of relational features. In addition, we collect a new Car Crash Dataset (CCD) for traffic accident anticipation which contains environmental attributes and accident reasons annotations. Experimental results on both public and the newly-compiled datasets show state-of-the-art performance of our model. Our code and CCD dataset are available at https://github.com/Cogito2012/UString.Comment: Accepted by ACM MM 202

Lower production of IL-17A and increased susceptibility to Mycobacterium bovis in mice coinfected with Strongyloides venezuelensis

The presence of intestinal helminths can down-regulate the immune response required to control mycobacterial infection. BALB/c mice infected with Mycobacterium bovis following an infection with the intestinal helminth Strongyloides venezuelensis showed reduced interleukin-17A production by lung cells and increased bacterial burden. Also, small granulomas and a high accumulation of cells expressing the inhibitory molecule CTLA-4 were observed in the lung. These data suggest that intestinal helminth infection could have a detrimental effect on the control of tuberculosis (TB) and render coinfected individuals more susceptible to the development of TB