RESUMO
Despite extensive research about parent-child attachment using observational and self-report studies, complementary measures are needed to assess this construct objectively with ecological validity, as well as less obtrusiveness and reactivity than traditional measures. This systematic review describes existing technology-based ecologically momentary assessment (EMA) tools examining attachment-related emotions, cognition, and behaviors between the child and its parents. From the study's inception until March 2021, four databases were searched resulting in 11,910 screened citations. Finally, 18 records were included, characterized by a broad variety of assessment tools, sample characteristics, study designs, and attachment outcomes. Technology-based EMA methods comprised audio, video, diary, and sensory assessment modalities, each occuying its methodological niche. When reported, the psychometric properties of the EMA methods were evaluated as very good; however, the included studies' psychometric data was not completely examined. The main attachment outcomes assessed by EMA were emotional and cognitive reactions and actions of the children, the parents, and the dyad. Cognition was rarely assessed using EMA methods. Future research should focus on the complexity of attachment considering different ethnic backgrounds, multiple caregivers' viewpoints, gender aspects, as well as cognitive and dyadic contents in the naturalistic environment.
Assuntos
Avaliação Momentânea Ecológica , Emoções , Humanos , Pais , Autorrelato , Relações Pais-FilhoRESUMO
Investigating the electrical double layer (EDL) structure has been a long-standing challenge and has seen the emergence of several sophisticated techniques able to probe selectively the few molecular layers of a solid/water interface. While a qualitative estimation of the thickness of the EDL can be obtained using simple theoretical models, following experimentally its evolution is not straightforward and can be even more complicated in nano- or microscale systems, particularly when changing the ionic concentration by several orders of magnitude. Here, we bring insight into the structure of the EDL of SiO2 nanoparticle suspensions and its evolution with increasing ionic concentration using angle-resolved second harmonic scattering (AR-SHS). Below millimolar salt concentrations, we can successively characterize inner-sphere adsorption, diffuse layer formation, and outer-sphere adsorption. Moreover, we show for the first time that, by appropriately selecting the nanoparticle size, it is possible to retrieve information also in the millimolar range. There, we observe a decrease in the magnitude of the surface potential corresponding to a compression in the EDL thickness, which agrees with the results of several other electroanalytical and optical techniques. Molecular dynamics simulations suggest that the EDL compression mainly results from the diffuse layer compression rather than outer-sphere ions (Stern plane) moving closer to the surface.
RESUMO
The acid-base properties of surfaces significantly influence catalytic and (photo)electrochemical processes. Estimation of acid dissociation constants (pKa values) for colloids is commonly performed through electroanalytical techniques or spectroscopic methods employing label molecules. Here, we show that polarimetric angle-resolved second harmonic scattering (AR-SHS) can be used as an all-optical, label-free probe of colloid surface pKa values. We apply AR-SHS to dispersions of 100 nm anatase TiO2 particles to extract surface potential and surface susceptibility, a measure of interfacial water orientation, as a function of pH. The surface potential follows changes in surface charge density, while the interfacial water orientation inverts at pH â¼4.8, â¼6, and â¼7.6. As the variation in bulk pH modifies the populations of Ti-OH2+, Ti-OH, and Ti-O- interfacial groups, a change in water orientation reports on the ratio of protonated/deprotonated species. Such observation allows for pKa evaluation from plots of surface susceptibility versus pH. A Nerstian trend in the surface potential is additionally demonstrated.
Assuntos
Nanopartículas , Água , Coloides/química , Titânio/química , Água/químicaRESUMO
Ion-specific effects play a crucial role in controlling the stability of colloidal systems and regulating interfacial processes. Although mechanistic pictures have been developed to explain the electrostatic structure of solid/water colloidal interfaces, ion-specific effects remain poorly understood. Here we quantify the average interfacial water orientation and the electrostatic surface potential around 100 nm SiO2 and TiO2 colloidal particles in the presence of NaCl, RbCl, and CaCl2 using polarimetric angle-resolved second harmonic scattering. We show that these two parameters can be used to establish the ion adsorption mechanism in a low ionic strength regime (<1 mM added salt). The relative differences between salts as a function of the ionic strength demonstrate cation- and surface-specific preferences for inner- vs outer-sphere adsorption. Compared to monovalent Rb+ and Na+, Ca2+ is found to be preferentially adsorbed as outer-sphere on SiO2 surfaces, while a dominant inner-sphere adsorption is observed for Ca2+ on TiO2. Molecular dynamics simulations performed on crystalline SiO2 and TiO2 surfaces support the experimental conclusions. This work contributes to the understanding of the electrostatic environment around colloidal nanoparticles on a molecular level by providing insight into ion-specific effects with micromolar sensitivity.
RESUMO
Colloidal nanoparticles exhibit unique size-dependentâ¯properties differing from their bulk counterpart, which can be particularly relevant for catalytic applications. To optimize surface-mediated chemical reactions, the understanding of the microscopic structure of the nanoparticle-liquid interface is of paramount importance. Here we use polarimetric angle-resolved second harmonic scattering (AR-SHS) to determine surface potential values as well as interfacial water orientation of â¼100 nm diameter amorphous TiO2 nanoparticles dispersed in aqueous solutions, without any initial assumption on the distribution of interfacial charges. We find three regions of different behavior with increasing NaCl concentration. At very low ionic strengths (0-10 µM), the Na+ ions are preferentially adsorbed at the TiO2 surface as inner-sphere complexes. At low ionic strengths (10-100 µM), a distribution of counterions equivalent to a diffuse layer is observed, while at higher ionic strengths (>100 µM), an additional layer of hydrated condensed ions is formed. We find a similar behavior for TiO2 nanoparticles in solutions of different basic pH. Compared to identically sized SiO2 nanoparticles, the TiO2 interface has a higher affinity for Na+ ions, which we further confirm with molecular dynamics simulations. With its ability to monitor ion adsorption at the surface with micromolar sensitivity and changes in the surface potential, AR-SHS is a powerful tool to investigate interfacial properties in a variety of catalytic and photocatalytic applications.
RESUMO
The microscopic description of the interface of colloidal particles in solution is essential to understand and predict the stability of these systems, as well as their chemical and electrochemical reactivity. However, this description often relies on the use of simplified electrostatic mean field models for the structure of the interface, which give only theoretical estimates of surface potential values and do not provide properties related to the local microscopic structure, such as the orientation of interfacial water molecules. Here we apply polarimetric angle-resolved second harmonic scattering (AR-SHS) to 300 nm diameter SiO2 colloidal suspensions to experimentally determine both surface potential and interfacial water orientation as a function of pH and NaCl concentration. The surface potential values and interfacial water orientation change significantly over the studied pH and salt concentration range, whereas zeta-potential (ζ) values remain constant. By comparing the surface and ζ-potentials, we find a layer of hydrated condensed ions present in the high pH case, and for NaCl concentrations ≥1 mM. For milder pH ranges (pH < 11), as well as for salt concentrations <1 mM, no charge condensation layer is observed. These findings are used to compute the surface charge densities using the Gouy-Chapman and Gouy-Chapman-Stern models. Furthermore, by using the AR-SHS data, we are able to determine the preferred water orientation in the layer directly in contact with the silica interface. Molecular dynamics simulations confirm the experimental trends and allow deciphering of the contributions of water layers to the total response.