Browsing by Author "Coutinho, J."
Now showing 1 - 3 of 3
Results Per Page
Sort Options
- Oxygen vacancies, the optical band gap (Eg) and photocatalysis ofhydroxyapatite: Comparing modelling with measured dataPublication . Bystrov, V. S.; Piccirillo, C.; Tobaldi, D. M.; Castro, P. M. L.; Coutinho, J.; Kopyl, S.; Pullar, R.Hydroxyapatite (Ca10(PO4)6(OH)2, HAp) is a calcium phosphate employed both in biomedicine and forenvironmental remediation. It is known that HAp can also be photocatalytic under UV light, probablydue to oxygen deficiencies, but the mechanism is unclear, and reported optical band gap energies varygreatly. For the first time we propose the mechanisms and precise kinds of vacancies which may causethe photocatalytic activity of HAp, and compare these theoretical data with our measured data on bothsamples of marine origin and commercial HAp powders. Density functional theory (DFT) (from firstprinciples calculations and Density of States (DOS) modelling) was used to calculate the optical bandgap energy (Eg) created by various possible oxygen vacancies in the HAp lattice: O from PO4, O fromOH, the loss of an entire OH group, or the simultaneous loss of O from PO4and an entire OH group. Themodelled values match the measured values very closely, suggesting that in non-photocatalytic HAp, ifany vacancies exist, they are O atoms from the OH group, resulting in a band gap of ∼5 eV in the UVCregion (not present in solar light at the Earth’s surface). However, in photocatalytic HAp, reduction fromthe combustion of an organic component at 1000◦C led to oxygen deficiency in the phosphate groups,probably in the O15 position, giving an Egof ∼3.45 eV, in the UVA region (present in sunlight). HeatingHAp with no organic component to 1200◦C also led to vacancies, of both an entire OH group and oxygenfrom PO4groups, which led to an intermediate Egvalue of ∼4 eV, on the boundary of the UVA-UVB regions.Absorption peaks were also predicted in the visible-light region with some types of vacancy.
- Psychophysiological reactivity in couples during a marital interaction taskPublication . Coutinho, J.; Oliveira-Silva, P.; Mesquita, A. R.; Barbosa, M.; Perrone-McGovern, K. M.; Gonçalves, O. F.The ability to regulate our own physiological arousal when dealing with the emotional expression of our partner is crucial for satisfactory and stable intimate relationships. In previous physiological studies of marital interactions, researchers have found greater levels of psychophysiological arousal for members of the couple in conflictual interactions in comparison with positive interactions. Past researchers have established that intense and prolonged autonomic and neuroendocrine arousal during marital conflict can have negative consequences for mental and physical health. In this study we examined the physiological reactivity, as measured by skin conductance level, heart rate and cortisol levels, from both partners during a couple's interaction task consisting of a structured conversation about positive and negative aspects of their relationship. Participants were thirty-two heterosexual couples (N = 64) in a committed monogamous relationship with a minimum duration of one year. We found higher heart rate and cortisol levels during negative interaction condition when compared with the positive condition. Skin conductance was higher in the positive interaction condition, when compared with the negative interaction condition. In addition, we found a significant negative association between heart rate variability and autonomic arousal evoked by the interaction task. The implications of these findings for the effects of marital strain on health as well as for the design of risk-reducing interventions, namely biofeedback are discussed.
- Surface modified hydroxyapatites with various functionalized nanostructures: computational studies of the vacancies in HApPublication . Bystrova, V. S.; Paramonova, E. V.; Bystrova, A. V.; Pullar, R. C.; Kopyl, S.; Tobaldi, D. M.; Piccirillo, C.; Avakyan, L. A.; Coutinho, J.Hydroxyapatite (HAp) has structural features that define its basic physical properties, which have an important role at the surface, and it is one of the most used materials in bone implants. In this work, we present a density functional modeling (DFT) study of HAp both as bulk and with special HAp models with various defects, especially oxygen vacancies in HAp surface layers, which can also determine photocatalytic properties, confirmed experimentally. The first-principles calculations of bulk and modified HAp were carried out using local basis (AIMPRO) and plane-wave (VASP) codes. Data obtained are analyzed using both approaches, and compared.