Application of NMR RDC’s, relaxation and self-diffusion for the study of dynamic processes of small molecules in solution

Spin-lattice Relaxation, self-Diffusion coefficients and Residual Dipolar Couplings (RDC’s) are the basis of well established Nuclear Magnetic Resonance techniques for the physicochemical study of small molecules (typically organic compounds and natural products with MW < 1000 Da), as they proved to be a powerful and complementary source of information about structural dynamic processes in solution. The work developed in this thesis consists in the application of the earlier-mentioned NMR techniques to explore, analyze and systematize patterns of the molecular dynamic behavior of selected small molecules in particular experimental conditions. Two systems were chosen to investigate molecular dynamic behavior by these techniques: the dynamics of ion-pair formation and ion interaction in ionic liquids (IL) and the dynamics of molecular reorientation when molecules are placed in oriented phases (alignment media). The application of NMR spin-lattice relaxation and self-diffusion measurements was applied to study the rotational and translational molecular dynamics of the IL: 1-butyl-3-methylimidazolium tetrafluoroborate [BMIM][BF4]. The study of the cation-anion dynamics in neat and IL-water mixtures was systematically investigated by a combination of multinuclear NMR relaxation techniques with diffusion data (using by H1, C13 and F19 NMR spectroscopy). Spin-lattice relaxation time (T1), self-diffusion coefficients and nuclear Overhauser effect experiments were combined to determine the conditions that favor the formation of long lived [BMIM][BF4] ion-pairs in water. For this purpose and using the self-diffusion coefficients of cation and anion as a probe, different IL-water compositions were screened (from neat IL to infinite dilution) to find the conditions where both cation and anion present equal diffusion coefficients (8% water fraction at 25 ºC). This condition as well as the neat IL and the infinite dilution were then further studied by 13C NMR relaxation in order to determine correlation times (c) for the molecular reorientational motion using a mathematical iterative procedure and experimental data obtained in a temperature range between 273 and 353 K. The behavior of self-diffusion and relaxation data obtained in our experiments point at the combining parameters of molar fraction 8 % and temperature 298 K as the most favorable condition for the formation of long lived ion-pairs. When molecules are subjected to soft anisotropic motion by being placed in some special media, Residual Dipolar Couplings (RDCs), can be measured, because of the partial alignment induced by this media. RDCs are emerging as a powerful routine tool employed in conformational analysis, as it complements and even outperforms the approaches based on the classical NMR NOE or J3 couplings. In this work, three different alignment media have been characterized and evaluated in terms of integrity using 2H and 1H 1D-NMR spectroscopy, namely the stretched and compressed gel PMMA, and the lyotropic liquid crystals CpCl/n-hexanol/brine and cromolyn/water. The influence that different media and degrees of alignment have on the dynamic properties of several molecules was explored. Different sized sugars were used and their self-diffusion was determined as well as conformation features using RDCs. The results obtained indicate that no influence is felt by the small molecules diffusion and conformational features studied within the alignment degree range studied, which was the 3, 5 and 6 % CpCl/n-hexanol/brine for diffusion, and 5 and 7.5 % CpCl/n-hexanol/brine for conformation. It was also possible to determine that the small molecules diffusion verified in the alignment media presented close values to the ones observed in water, reinforcing the idea of no conditioning of molecular properties in such media.

A matter of time: Phases of customer co-creation community participation and their impact on customer behavior

Despite the growing relevance of co-creating customer communities only little scientific evidence is available on their impact on transactional behavior of participants. Previous research has mostly used self-reported data or distinguished only between during and pre-community phases obtaining mixed results. However, the author proposes that co-creating community activity takes place in five distinguishable phases and changes in transactional behavior are limited to certain phases. Using 33 months of transactional data of a Dutch online auction provider a study was conducted covering all five phases of the community co-creation process from community planning over community set-up, co-development and co-testing to post-launch. The overall results indicate mixed effects of community participation on the different transactional variables during the co-creation process. Community participation had positive effects on auctions listing behavior at the community set-up, co-development and post-launch phases, whereby the number of auctions listed peaked during the community set-up phase. These results suggest that the impact on transactional behavior differs between co-creation phases and different psychological mechanism limited to certain phases might trigger the respective changes.

Effect of surface plasmon resonance in TiO2/Au thin films on the fluorescence of self-assembled CdTe QDs structure

The exceptional properties of localised surface plasmons (LSPs), such as local field enhancement and confinement effects, resonant behavior, make them ideal candidates to control the emission of luminescent nanoparticles. In the present work, we investigated the LSP effect on the steady-state and time-resolved emission properties of quantum dots (QDs) by organizing the dots into self-assembled dendrite structures deposited on plasmonic nanostructures. Self-assembled structures consisting of water-soluble CdTe mono-size QDs, were developed on the surface of co-sputtered TiO2 thin films doped with Au nanoparticles (NPs) annealed at different temperatures. Their steady-state fluorescence properties were probed by scanning the spatially resolved emission spectra and the energy transfer processes were investigated by the fluorescence lifetime imaging (FLIM) microscopy. Our results indicate that a resonant coupling between excitons confined in QDs and LSPs in Au NPs located beneath the self-assembled structure indeed takes place and results in (i) a shift of the ground state luminescence towards higher energies and onset of emission from excited states in QDs, and (ii) a decrease of the ground state exciton lifetime (fluorescence quenching).

Concrete with triphasic conductive materials for self-monitoring of cracking development subjected to flexure

In this study, the macro steel fiber (SF), carbon fiber (CF) and nano carbon black (NCB) as triphasic conductive materials were added into concrete, in order to improve the conductivity and ductility of concrete. The influence of NCB, SF and CF on the post crack behavior and conductivity of concrete was explored. The effect of the triphasic conductive materials on the self-diagnosing ability to the load–deflection property and crack widening of conductive concrete member subjected to bending were investigated. The relationship between the fractional change in surface impedance (FCR) and the crack opening displacement (COD) of concrete beams with conductive materials has been established. The results illustrated that there is a linear relationship between COD and FCR.

The effects of introducing the Amazonian squirrel monkey on the behavior of the northeast marmoset

The squirrel monkey Saimiri sciureus, an endemic primate of the Amazonian Basin, has been introduced in many localities of the Atlantic Forest biome. Introduced exotic species gain a competitive advantage in their new environment because of a lack of natural predators, competitors or diseases. This advantage can result in a reduction in the resources for the endemic species. The aims of this work were to evaluate the level of adaptation, and monitor the forms of interaction and the impact caused by S. sciureus on the behavior of the native species Callithrix jacchus in the Saltinho Biological Reserve, Tamandaré, Pernambuco, Brazil. The behavior was assessed by use of scan sampling method, every 5 min. A total of 382 h (191 h or 2,292 scans per group) of time sampling was performed. Sixteen interactions were recorded. The interaction index was low and represented 2.4% of the total observation time. Interactions were significantly higher during the dry season (58.5%) relative to the rainy season (41.5%). Callithrix jacchus was intolerant to the presence of S. sciureus and the last one was more tolerant during the interactions. In the presence of S. sciureus, C. jacchus eating, foraging, resting, socializing, and self-grooming behaviors were reduced while alertness was increased. Territorial behavior showed no significant difference. In the presence of S. sciureus, on average, the group of marmosets assembled at a higher layer of the forest stratum. The results might indicate a negative effect of S. sciureus on the native species, C. jacchus.

Eating habits and psychopathology: translation, adaptation, reliability of the Nutrition Behavior Inventory to Portuguese and relation to psychopathology

Objective: The Nutrition-Behavior Inventory (NBI) is a self-administered instrument that allows eating habits to be correlated with psychopathological symptoms. The objective was to translate and adapt the NBI to Portuguese, and test the Portuguese NBI’s reliability. The second aim was to verify its sensitivity for identification of risk factors in terms of behavior/eating habits in children and adolescents. Methods: The NBI was translated, adapted, and back-translated. The Portuguese version of the NBI was then applied (N = 96; 9-12 years). In order to verify the internal consistency, Cronbach’s alpha was used. The psychopathological indicators of the participants were accessed using the Child Behavior Checklist (CBCL). The mean CBCL scores were analyzed in relation to the NBI data (cutoff point: ≥ 30 with indicators, and < 30 without). Results: Internal consistency was high (Cronbach’s alpha = 0.89) for the NBI. The CBCL scores correlated significantly with NBI (> 30) on the following: anxiety and depression (p = 0.041), social difficulties (p = 0.028), attention problems (p = 0.001), aggressive behavior (p = 0.015); ADHD (p < 0.001), and conduct problems (p = 0.032). Conclusion: The present results indicate that the NBI is a reliable instrument. The NBI can be useful for evaluating psychopathological symptoms related to the eating habits and behaviors of children and adolescents.

The effect of high-fat diet on rat’s mood, feeding behavior and response to stress

An association between obesity and depression has been indicated in studies addressing common physical (metabolic) and psychological (anxiety, low self-esteem) outcomes. Of consideration in both obesity and depression are chronic mild stressors to which individuals are exposed to on a daily basis. However, the response to stress is remarkably variable depending on numerous factors, such as the physical health and the mental state at the time of exposure. Here a chronic mild stress (CMS) protocol was used to assess the effect of high-fat diet (HFD)-induced obesity on response to stress in a rat model. In addition to the development of metabolic complications, such as glucose intolerance, diet-induced obesity caused behavioral alterations. Specifically, animals fed on HFD displayed depressive- and anxious-like behaviors that were only present in the normal diet (ND) group upon exposure to CMS. Of notice, these mood impairments were not further aggravated when the HFD animals were exposed to CMS, which suggest a ceiling effect. Moreover, although there was a sudden drop of food consumption in the first 3 weeks of the CMS protocol in both ND and HFD groups, only the CMS-HFD displayed an overall noticeable decrease in total food intake during the 6 weeks of the CMS protocol. Altogether, the study suggests that HFD impacts on the response to CMS, which should be considered when addressing the consequences of obesity in behavior.

Self-esteem, assertiveness and resilience in adolescents institutionalized

The institutionalization of children and adolescents has been an increasingly visible problem in modern society. Unfavourable socio-economic conditions have been joining the behavior problems and school absenteeism. When the family fails in its competence for education, social security or the Court withdraws the child or adolescent to a host institution. The aim of this research was to characterize self-esteem, assertiveness and resilience of institutionalized adolescents in the northern region of Portugal and to establish associations with these dependent variables and gender, scholar level and duration of the institutionalization. For the purpose of this study a wider questionnaire was carried out, and validated with a smaller group. It was a transversal study following a predominantly quantitative methodology, with a convenience sample. The sample included 101 adolescents (55 female and 46 males) from eight institutions, aged between 11 to 21 years old (average 15.45). For self-esteem the Rosenberg Self-Esteem Scale (Rosenberg, 1965), already validate for Portuguese adolescents, was used. For assertiveness and resilience it was applied the Global Evaluation Scale of Assertiveness and the Global Evaluation Scale of Resilience (Jardim & Pereira, 2006) we previously adapted and validated for adolescents. Collected data was introduced in a SPSS database. A descriptive analysis was done to characterize the sample concerning all the variables. To establish associations between individual factors and dependent variables t test, correlations and non-parametric test were applied. Results indicated a relatively low self-esteem (28.03), with girls having a lower value than boys, without significant differences. No correlations were found between self-esteem and the time in the institution. Assertiveness of the sample is average (23.97) and higher for girls than boys, with a positive significant correlation with the scholar grade. Also the resilience is average (25.97), having girls a little lower mean than boys and no significant differences or correlations were found.

Contractive probability metrics and asymptotic behavior of dissipative kinetic equations

The present notes are intended to present a detailed review of the existing results in dissipative kinetic theory which make use of the contraction properties of two main families of probability metrics: optimal mass transport and Fourier-based metrics. The first part of the notes is devoted to a self-consistent summary and presentation of the properties of both probability metrics, including new aspects on the relationships between them and other metrics of wide use in probability theory. These results are of independent interest with potential use in other contexts in Partial Differential Equations and Probability Theory. The second part of the notes makes a different presentation of the asymptotic behavior of Inelastic Maxwell Models than the one presented in the literature and it shows a new example of application: particle's bath heating. We show how starting from the contraction properties in probability metrics, one can deduce the existence, uniqueness and asymptotic stability in classical spaces. A global strategy with this aim is set up and applied in two dissipative models.

Corticosterone shifts reproductive behaviour towards self-maintenance in the barn owl and is linked to melanin-based coloration in females.

Trade-offs between the benefits of current reproduction and the costs to future reproduction and survival are widely recognized. However, such trade-offs might only be detected when resources become limited to the point where investment in one activity jeopardizes investment in others. The resolution of the trade-off between reproduction and self-maintenance is mediated by hormones such as glucocorticoids which direct behaviour and physiology towards self-maintenance under stressful situations. We investigated this trade-off in male and female barn owls in relation to the degree of heritable melanin-based coloration, a trait that reflects the ability to cope with various sources of stress in nestlings. We increased circulating corticosterone in breeding adults by implanting a corticosterone-releasing-pellet, using birds implanted with a placebo-pellet as controls. In males, elevated corticosterone reduced the activity (i.e. reduced home-range size and distance covered within the home-range) independently of coloration, while we could not detect any effect on hunting efficiency. The effect of experimentally elevated corticosterone on female behaviour was correlated with their melanin-based coloration. Corticosterone (cort-) induced an increase in brooding behaviour in small-spotted females, while this hormone had no detectable effect in large-spotted females. Cort-females with small eumelanic spots showed the normal body-mass loss during the early nestling period, while large spotted cort-females did not lose body mass. This indicates that corticosterone induced a shift towards self-maintenance in males independently on their plumage, whereas in females this shift was observed only in large-spotted females.

Point-occurrence self-similarity in crackling-noise systems and in other complex systems

It has been recently found that a number of systems displaying crackling noise also show a remarkable behavior regarding the temporal occurrence of successive events versus their size: a scaling law for the probability distributions of waiting times as a function of a minimum size is fulfilled, signaling the existence on those systems of self-similarity in time-size. This property is also present in some non-crackling systems. Here, the uncommon character of the scaling law is illustrated with simple marked renewal processes, built by definition with no correlations. Whereas processes with a finite mean waiting time do not fulfill a scaling law in general and tend towards a Poisson process in the limit of very high sizes, processes without a finite mean tend to another class of distributions, characterized by double power-law waiting-time densities. This is somehow reminiscent of the generalized central limit theorem. A model with short-range correlations is not able to escape from the attraction of those limit distributions. A discussion on open problems in the modeling of these properties is provided.

Who is the fairest of them all? The independent effect of attractive features and self-perceived attractiveness on cooperation among women

The present paper analyzes the extent to which attractiveness-related variables affect cooperative behavior in women. Cooperativeness is evaluated through a Prisoner's Dilemma Game (PDG). We consider several morphometric variables related to attractiveness: Fluctuating Asymmetry (FA), Waist-Hip Ratio (WHR, Body Mass Index (BMI) and Facial Femininity (FF). These variables have been shown to predict human behavior. We also include as a control variable a score for Self-Perceived Attractiveness (SPA). We test differences in these variables according to behavior in the PDG. Our results reveal that low FA women cooperate less frequently in the PDG. We also find that women with lower WHR are more cooperative. This result contradicts the expected relation between WHR and behavior in the PDG. We show that this effect of WHR on cooperation operates through its influence on the expectation that participants hold on the cooperative intent of their counterpart. In addition, we show that the effect of attractive features on cooperation occurs independently of the participants' perception of their own appeal. Finally, we discuss our results in the context of the evolution of cooperative behavior and under the hypothesis that attractiveness is a reliable indicator of phenotypic quality.

Sexual protection behavior in HIV-positive gay men: testing a modified information-motivation-behavioral skills model.

This study on determinants of sexual protection behavior among HIV-positive gay men used the empirically tested information-motivation-behavioral skills (IMB) model. HIV-specific variables were added to the model to determine factors decisive for condom use with steady and casual partners. Data were collected using an anonymous, standardized self-administered questionnaire. Study participants were recruited at HIV outpatient clinics associated with the Eurosupport Study Group and the Swiss HIV Cohort Study. To identify factors associated with condom use, backward elimination regression analyses were performed. Overall, 838 HIV-infected gay men from 14 European countries were included in this analysis. About 53% of them reported at least one sexual contact with a steady partner; 62.5% had sex with a casual partner during the last 6 months. Forty-three percent always used condoms with steady partners and 44% with casual partners. High self-efficacy and subjective norms in favor of condom-use were associated with increased condom use with casual and steady partners, whereas feeling depressed was associated with decreased condom use with casual partners. Condoms were used less often with HIV-positive partners. Self-efficacy as an important behavioral skill to perform protection behavior was influenced by lower perceived vulnerability, higher subjective norms, and more positive safer sex attitudes. The IMB-model constructs appeared to be valid; however, not all the model predictors could be determined as hypothesized. Besides the original IMB constructs, HIV-specific variables, including sexual partners' serostatus and mental health, explained condom use. Such factors should be considered in clinical interventions to promote "positive prevention."

Trends in self-reported prevalence and management of hypertension, dyslipidaemia and diabetes in adults in Switzerland, 1992-2007

Purpose: to assess the trends of self-reported prevalence of cardiovascular risk factors (CV RFs: hypertension, dyslipidaemia, diabetes) and their management for period 1992 to 2007 in the Swiss population. Methods: four National health interview surveys conducted between 1992 and 2007 in representative samples of the Swiss population (63,782 subjects overall). Self-reported CV RFs prevalence, treatment and controllevels were computed after weighting. Weights were calculated by raking ratio such that the marginal distribution of the weighted totals conforms to the marginal distribution of the targeted population. Multivariate analysis adjusted on age, sex, education, nationality and SMI was conducted using logistic regression. Results: prevalence of ail CV RFs increased between 1992 and 2007, see table. Although the self-reported prevalence of treatment among subjects with CV RFs increased, and this was confirmed by multivariate analysis: OR for hypocholesterolaemic treatment relative to 1992: 0.64 [0.52-0.78]; 1.39 [1.18-1.65] and 2.00 [1.69-2.36] for 1997, 2002 and 2007, respectively. Still, in 2007, circa 40% of hypertensive, 60% of dyslipidaemic and 50% of diabetic subjects weren't treated. Conversely, an adequate control of CV RFs was reported by treated subjects, with an increase during the study period. This increase was confirmed by multivariate analysis (not shown). Conclusion: the self-reported prevalence of hypertension, dyslipidaemia and diabetes increased between 1992 and 2007 in the Swiss population. Despite a good control of treated subjects, still a significant percentage of subjects with CV RFs are not treated.