We investigate the characteristics, fate and photocatalytic activity of spheroid- and rod-shaped TiO2 nano-crystals in aqueous solutions to better understand their behaviour in media of biological and environmental interest. For this purpose, the potential of a solvothermal method in synthesizing highly crystalline nanoparticles and tuning their sizes/shapes is explored. Spheroid- and rod-shaped nanoparticles are successfully obtained with different aspect ratios, while keeping their structures as well as their cross-sectional areas identical. The aggregation/agglomeration of these nanostructures in aqueous solutions shows an obvious shape effect, revealing critical coagulation concentrations (CCCs) significantly lower for the rods compared to the spheroids (aspect ratio ∼ 2-3). This trend is observed in both NaCl and CaCl2 electrolytes at pH values above and below the pHPZC of TiO2 nanoparticles. The photocatalytic activity of the spheroids is unexpectedly superior to that of the rods at NaCl and CaCl2 concentrations over a range of 2 to 100 and 1 to 50 mM, respectively. Our results show that an increase in the chloride concentration leads to an inhibition of the photocatalytic activity rate, with a more pronounced impact for the rods. In contrast, the size of aggregates/agglomerates has only a little effect on the photocatalytic properties of both nano-crystals.
The adsorption behavior of collagen on solid surfaces is a process that determines the role of this protein to mediate cell–material interaction. Herein, the mechanism of self‐assembly and organization of collagen on a model substrate is investigated in the presence of TiO2 nanoparticles. In solution, results show that nanoparticles do not alter the conformation of collagen (triple‐helix), and slightly delay the kinetics of its self‐assembly. In the adsorbed state, by exploring the dewetting patterns of collagen layers from atomic force microscopy (AFM) images, a method is developed to extract parameters describing the characteristics of collagen networks. It is shown that collagen layer is strongly impacted by the presence of nanoparticles in the medium. These results are consistent with the analysis of the protein layers in the hydrated state, showing a rigidification, as observed by quartz crystal microbalance with dissipation monitoring (QCM‐D), and the formation of shorter and/or less extended fibrillar structures with a lower surface density, as probed by AFM force spectroscopy. The approach described here provides a reconciliation between disparate views of collagen layers' characterization in the dried and the hydrated states. It also offers new perspectives to assess the impact of nanoparticles on the organization of collagen during in vitro tests, particularly at the stage of cell adhesion.
Correction for ‘Factors impacting the aggregation/agglomeration and photocatalytic activity of highly crystalline spheroid- and rod-shaped TiO2 nanoparticles in aqueous solutions’ by Thomas Degabriel, Elodie Colaço et al., Phys. Chem. Chem. Phys., 2018, 20, 12898–12907, https://doi.org/10.1039/C7CP08054A.
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