Effect of acid or alkaline catalyst and of different capping agents on the optical properties of CdS nanoparticles incorporated within a diureasil hybrid matrix

CdS nanoparticles (NPs) were synthesized using colloidal methods and incorporated within a diureasil hybrid matrix. The surface capping of the CdS NPs by 3-mercaptopropyltrimethoxysilane (MPTMS) and 3-aminopropyltrimethoxysilane (APTMS) organic ligands during the incorporation of the NPs within the hybrid matrix has been investigated. The matrix is based on poly(ethylene oxide)/poly(propylene oxide) chains grafted to a siliceous skeleton through urea bonds and was produced by sol–gel process. Both alkaline and acidic catalysis of the sol–gel reaction were used to evaluate the effect of each organic ligand on the optical properties of the CdS NPs. The hybrid materials were characterized by absorption, steady-state and time-resolved photoluminescence spectroscopy and High Resolution Transmission Electron Microscopy (HR-TEM). The preservation of the optical properties of the CdS NPs within the diureasil hybrids was dependent on the experimental conditions used. Both organic ligands (APTMS and MPTMS) demonstrated to be crucial in avoiding the increase of size distribution and clustering of the NPs within the hybrid matrix. The use of organic ligands was also shown to influence the level of interaction between the hybrid host and the CdS NPs. The CdS NPs showed large Stokes shifts and long average lifetimes, both in colloidal solution and in the xerogels, due to the origin of the PL emission in surface states. The CdS NPs capped with MPTMS have lower PL lifetimes compared to the other xerogel samples but still larger than the CdS NPs in the original colloidal solution. An increase in PL lifetimes of the NPs after their incorporation within the hybrid matrix is related to interaction between the NPs and the hybrid host matrix.

Electronic structure and optical signatures of semiconducting transition metal dichalcogenide nanosheets

CONSPECTUS: Two-dimensional (2D) crystals derived from transition metal dichalcogenides (TMDs) are intriguing materials that offer a unique platform to study fundamental physical phenomena as well as to explore development of novel devices. Semiconducting group 6 TMDs such as MoS2 and WSe2 are known for their large optical absorption coefficient and their potential for high efficiency photovoltaics and photodetectors. Monolayer sheets of these compounds are flexible, stretchable, and soft semiconductors with a direct band gap in contrast to their well-known bulk crystals that are rigid and hard indirect gap semiconductors. Recent intense research has been motivated by the distinct electrical, optical, and mechanical properties of these TMD crystals in the ultimate thickness regime. As a semiconductor with a band gap in the visible to near-IR frequencies, these 2D MX2 materials (M = Mo, W; X = S, Se) exhibit distinct excitonic absorption and emission features. In this Account, we discuss how optical spectroscopy of these materials allows investigation of their electronic properties and the relaxation dynamics of excitons. We first discuss the basic electronic structure of 2D TMDs highlighting the key features of the dispersion relation. With the help of theoretical calculations, we further discuss how photoluminescence energy of direct and indirect excitons provide a guide to understanding the evolution of the electronic structure as a function of the number of layers. We also highlight the behavior of the two competing conduction valleys and their role in the optical processes. Intercalation of group 6 TMDs by alkali metals results in the structural phase transformation with corresponding semiconductor-to-metal transition. Monolayer TMDs obtained by intercalation-assisted exfoliation retains the metastable metallic phase. Mild annealing, however, destabilizes the metastable phase and gradually restores the original semiconducting phase. Interestingly, the semiconducting 2H phase, metallic 1T phase, and a charge-density-wave-like 1T' phase can coexist within a single crystalline monolayer sheet. We further discuss the electronic properties of the restacked films of chemically exfoliated MoS2. Finally, we focus on the strong optical absorption and related exciton relaxation in monolayer and bilayer MX2. Monolayer MX2 absorbs as much as 30% of incident photons in the blue region of the visible light despite being atomically thin. This giant absorption is attributed to nesting of the conduction and valence bands, which leads to diversion of optical conductivity. We describe how the relaxation pathway of excitons depends strongly on the excitation energy. Excitation at the band nesting region is of unique significance because it leads to relaxation of electrons and holes with opposite momentum and spontaneous formation of indirect excitons.

Biological behaviour of thin films consisting of Au nanoparticles dispersed in a TiO2 dielectric matrix

In this work it was studied the possible use of thin films, composed of Au nanoparticles (NPs) embedded in a TiO2 matrix, in biological applications, by evaluating their interaction with a well-known protein, Bovine Serum Albumin (BSA), as well as with microbial cells (Candida albicans). The films were produced by one-step reactive DC magnetron sputtering followed by heat-treatment. The samples revealed a composition of 8.3 at.% of Au and a stoichiometric TiO2 matrix. The annealing promoted grain size increase of the Au NPs from 3 nm (at 300 °C) to 7 nm (at 500 °C) and a progressive crystallization of the TiO2 matrix to anatase. A broad localized surface plasmon resonance (LSPR) absorption band (λ = 580–720 nm) was clearly observed in the sample annealed at 500 °C, being less intense at 300 °C. The biological tests indicated that the BSA adhesion is dependent on surface nanostructure morphology, which in turn depends on the annealing temperature that changed the roughness and wettability of the films. The Au:TiO2 thin films also induced a significant change of the microbial cell membrane integrity, and ultimately the cell viability, which in turn affected the adhesion on its surface. The microstructural changes (structure, grain size and surface morphology) of the Au:TiO2 films promoted by heat-treatment shaped the amount of BSA adhered and affected cell viability.

Acetylated bacterial cellulose coated with urinary bladder matrix as a substrate for retinal pigment epithelium

This work evaluated the effect of acetylated bacterial cellulose (ABC) substrates coated with urinary bladder matrix (UBM) on the behavior of Retinal Pigment Epithelium (RPE), as assessed by cell adhesion, proliferation and development of cell polarity exhibiting transepithelial resistance and polygonal shaped-cells with microvilli. Acetylation of bacterial cellulose (BC) generated a moderate hydrophobic surface (around 65°) while the adsorption of UBM onto these acetylated substrates did not affect significantly the surface hydrophobicity. The ABS substrates coated with UBM enabled the development of a cell phenotype closer to that of native RPE cells. These cells were able to express proteins essential for their cytoskeletal organization and metabolic function (ZO-1 and RPE65), while showing a polygonal shaped morphology with microvilli and a monolayer configuration. The coated ABC substrates were also characterized, exhibiting low swelling effect (between 1.52.0 swelling/mm3), high mechanical strength (2048 MPa) and non-pyrogenicity (2.12 EU/L). Therefore, the ABC substrates coated with UBM exhibit interesting features as potential cell carriers in RPE transplantation that ought to be further explored.

Elaboration et caractérisation des nanocristaux de Zn F O enfouis 1-x x dans des diélectriques pour des applications en spin-électronique

Tese de Doutoramento em Ciências - Especialidade em Física

Global validation of the WSES Sepsis Severity Score for patients with complicated intra-abdominal infections: a prospective multicentre study (WISS Study).

BACKGROUND To validate a new practical Sepsis Severity Score for patients with complicated intra-abdominal infections (cIAIs) including the clinical conditions at the admission (severe sepsis/septic shock), the origin of the cIAIs, the delay in source control, the setting of acquisition and any risk factors such as age and immunosuppression. METHODS The WISS study (WSES cIAIs Score Study) is a multicenter observational study underwent in 132 medical institutions worldwide during a four-month study period (October 2014-February 2015). Four thousand five hundred thirty-three patients with a mean age of 51.2 years (range 18-99) were enrolled in the WISS study. RESULTS Univariate analysis has shown that all factors that were previously included in the WSES Sepsis Severity Score were highly statistically significant between those who died and those who survived (p < 0.0001). The multivariate logistic regression model was highly significant (p < 0.0001, R2 = 0.54) and showed that all these factors were independent in predicting mortality of sepsis. Receiver Operator Curve has shown that the WSES Severity Sepsis Score had an excellent prediction for mortality. A score above 5.5 was the best predictor of mortality having a sensitivity of 89.2 %, a specificity of 83.5 % and a positive likelihood ratio of 5.4. CONCLUSIONS WSES Sepsis Severity Score for patients with complicated Intra-abdominal infections can be used on global level. It has shown high sensitivity, specificity, and likelihood ratio that may help us in making clinical decisions.

Investigating a galactomannan gel obtained from Cassia grandis seeds as immobilizing matrix for Cramoll lectin

Characterization, with emphasis on the rheological properties, of Cassia grandis seeds galactomannan gel containing immobilized Cramoll 1,4 is presented. The gels, with and without immobilized Cramoll 1,4, were evaluated along time by rheometry, pH, color, microbial contamination and lectin hemagglutinating activity (HA). Rheological determinations confirmed the gels to be very stable up to 30 days with variations occurring after this period. Rheological data also showed that the gel/Cramoll 1,4 immobilizing matrix loses its elastic modulus substantially after 60 days. Both gels presented no microbial contamination as well as a pH close to neutral. Colorimetric parameters demonstrated the gels transparency with occasional yellowness. The opacity of the galactomannan gel did not change significantly along the study; the same did not occur for the gel with immobilized Cramoll 1,4 as a statistically significant reduction of its opacity was observed. In what concerns immobilized Cramoll 1,4HA, up to 90% of its initial HA was maintained after 20 days, with a decrease to 60% after 60 days. These results combined with the thickening and stabilizing characteristics of the galactomannan gel make this gel a promising immobilizing matrix for Cramoll 1,4 that can be further exploited for clinical and cosmetic applications.

Determinação de psicofármacos em cabelo humano por técnicas cromatográficas hifenadas: um método alternativo não-invasivo

Dissertação de mestrado em Técnicas de Caracterização e Análise Química

Breastfeeding and depression: a systematic review of the literature

Background: Research has separately indicated associations between pregnancy depression and breastfeeding, breastfeeding and postpartum depression, and pregnancy and postpartum depression. This paper aimed to provide a systematic literature review on breastfeeding and depression, considering both pregnancy and postpartum depression. Methods: An electronic search in three databases was performed using the keywords: “breast feeding”, “bottle feeding”, “depression”, “pregnancy”, and “postpartum”. Two investigators independently evaluated the titles and abstracts in a first stage and the full-text in a second stage review. Papers not addressing the association among breastfeeding and pregnancy or postpartum depression, non-original research and research focused on the effect of antidepressants were excluded. 48 studies were selected and included. Data were independently extracted. Results: Pregnancy depression predicts a shorter breastfeeding duration, but not breastfeeding intention or initiation. Breastfeeding duration is associated with postpartum depression in almost all studies. Postpartum depression predicts and is predicted by breastfeeding cessation in several studies. Pregnancy and postpartum depression are associated with shorter breastfeeding duration. Breastfeeding may mediate the association between pregnancy and postpartum depression. Pregnancy depression predicts shorter breastfeeding duration and that may increase depressive symptoms during postpartum. Limitations: The selected keywords may have led to the exclusion of relevant references. Conclusions: Although strong empirical evidence regarding the associations among breastfeeding and pregnancy or postpartum depression was separately provided, further research, such as prospective studies, is needed to clarify the association among these three variables. Help for depressed pregnant women should be delivered to enhance both breastfeeding and postpartum psychological adjustment.

Sleep during the third trimester of pregnancy: the role of depression and anxiety

Depression has been associated with sleep disturbances in pregnancy; however, no previous research has controlled the possible confounding effect of anxiety on this association. This study aims to analyze the effect of depression on sleep during the third trimester of pregnancy controlling for anxiety. The sample was composed by 143 depressed (n = 77) and non-depressed (n = 66) pregnant women who completed measures of depression, anxiety, and sleep. Differences between groups in sleep controlling for anxiety were found. Depressed pregnant women present higher number of nocturnal awakenings and spent more hours trying falling asleep during the night and the entire 24 h period. Present findings point out the effect of depression on sleep in late pregnancy, after controlling for anxiety.

Breastfeeding is negatively affected by prenatal depression and reduces postpartum depression

Background. This prospective cohort study explored the effects of prenatal and postpartum depression on breastfeeding and the effect of breastfeeding on postpartum depression. Method. The Edinburgh Postpartum Depression Scale (EPDS) was administered to 145 women at the first, second and third trimester, and at the neonatal period and 3 months postpartum. Self-report exclusive breastfeeding since birth was collected at birth and at 3, 6 and 12 months postpartum. Data analyses were performed using repeated-measures ANOVAs and logistic and multiple linear regressions. Results. Depression scores at the third trimester, but not at 3 months postpartum, were the best predictors of exclusive breastfeeding duration (β =−0.30, t=−2.08, p<0.05). A significant decrease in depression scores was seen from childbirth to 3 months postpartum in women who maintained exclusive breastfeeding for53 months (F1,65 =3.73, p<0.10, ηp 2 =0.05). Conclusions. These findings suggest that screening for depression symptoms during pregnancy can help to identify women at risk for early cessation of exclusive breastfeeding, and that exclusive breastfeeding may help to reduce symptoms of depression from childbirth to 3 months postpartum.

Breastfeeding and postpartum depression: state of the art review

Objective: To review the literature on the association between breastfeeding and postpartum depression. Sources: A review of literature found on MEDLINE/ PubMed database. Summary of findings: The literature consistently shows that breastfeeding provides a wide range of benefits for both the child and the mother. The psychological benefits for the mother are still in need of further research. Some studies point out that pregnancy depression is one of the factors that may contribute to breastfeeding failure. Others studies also suggest an association between breastfeeding and postpartum depression; the direction of this association is still unclear. Breastfeeding can promote hormonal processes that protect mothers against postpartum depression by attenuating cortisol response to stress. It can also reduce the risk of postpartum depression, by helping the regulation of sleep and wake patterns for mother and child, improving mother’s self efficacy and her emotional involvement with the child, reducing the child’s temperamental difficulties, and promoting a better interaction between mother and child. Conclusions: Studies demonstrate that breastfeeding can protect mothers from postpartum depression, and are starting to clarify which biological and psychological processes may explain this protection. However, there are still equivocal results in the literature that may be explained by the methodological limitations presented by some studies.

Mother’s depression at childbirth does not contribute to the effects of antenatal depression on neonate’s behavioral development

Background: Maternal depression is a worldwide phenomenon that has been linked to adverse developmental outcomes in neonates. Aims: To study the effect of antenatal depression (during the third trimester of pregnancy) on neonate behavior, preference, and habituation to both the mother and a stranger’s face/voice. To analyze mother’s depression at childbirth as a potential mediator or moderator of the relationship between antenatal depression and neonate behavioral development. Method: A sample of 110 pregnant women was divided in 2 groups according to their scores on the Edinburgh Postnatal Depression Scale during pregnancy (EPDS; ≥10, depressed; <10, non-depressed). In the first 5 days after birth, neonatal performance on the Neonatal Behavioral Assessment Scale (NBAS) and in the ‘Preference and habituation to the mother’s face/voice versus stranger’ paradigm was assessed; each mother filled out an EPDS. Results: Neonates of depressed pregnant women, achieved lower scores on the NBASs (regulation of state, range of state, and habituation); did not show a visual/auditory preference for the mother’s face/voice; required more trials to become habituated to the mother’s face/voice; and showed a higher visual/auditory preference for the stranger’s face/voice after habituation compared to neonates of non-depressed pregnant women. Depression at childbirth does not contribute to the effect of antenatal depression on neonatal behavioral development. Conclusion: Depression even before childbirth compromises the neonatal behavioral development. Depression is a relevant issue and should be addressed as a routine part of prenatal health care.

Physical activity, health-related quality of life and depression during pregnancy

This study examines physical activity patterns among women, from pre-pregnancy to the second trimester of pregnancy, and the relationship between physical activity status based on physical activity guidelines and health-related quality of life (HRQoL) and depression over pregnancy. 56 healthy pregnant women self reported physical activity, HRQoL and depression at 10-15 and 19-24 weeks of pregnancy and physical activity before pregnancy. Whereas vigorous leisure physical activity decreased after conception, moderate leisure physical activity and work related physical activity remained stable over time. The prevalence of recommended physical activity was 39.3% and 12.5% in the 1st and 2nd trimesters of pregnancy respectively, and 14.3% pre-pregnancy. From the 1st to the 2nd pregnancy trimester, most physical HRQoL dimensions scores decreased and only mental component increased, independently of physical activity status. No changes in mean depression scores were observed. These data suggest that physical activity patterns change with pregnancy and that physical and mental components are differentially affected by pregnancy course, independently of physical activity status.

Hierarchical modelling of timber reference properties using probabilistic methods: Maximum Likelihood Method, Bayesian Methods and Probability Networks

In recent decades, an increased interest has been evidenced in the research on multi-scale hierarchical modelling in the field of mechanics, and also in the field of wood products and timber engineering. One of the main motivations for hierar-chical modelling is to understand how properties, composition and structure at lower scale levels may influence and be used to predict the material properties on a macroscopic and structural engineering scale. This chapter presents the applicability of statistic and probabilistic methods, such as the Maximum Likelihood method and Bayesian methods, in the representation of timber’s mechanical properties and its inference accounting to prior information obtained in different importance scales. These methods allow to analyse distinct timber’s reference properties, such as density, bending stiffness and strength, and hierarchically consider information obtained through different non, semi or destructive tests. The basis and fundaments of the methods are described and also recommendations and limitations are discussed. The methods may be used in several contexts, however require an expert’s knowledge to assess the correct statistic fitting and define the correlation arrangement between properties.