Multi-Scale Modelling of Aggregation of TiO2 Nanoparticle Suspensions in Water.

Titanium dioxide nanoparticles have risen concerns about their possible toxicity and the European Food Safety Authority recently banned the use of TiO2 nano-additive in food products. Following the intent of relating nanomaterials atomic structure with their toxicity without having to conduct large-scale experiments on living organisms, we investigate the aggregation of titanium dioxide nanoparticles using a multi-scale technique: starting from ab initio Density Functional Theory to get an accurate determination of the energetics and electronic structure, we switch to classical Molecular Dynamics simulations to calculate the Potential of Mean Force for the connection of two identical nanoparticles in water; the fitting of the latter by a set of mathematical equations is the key for the upscale. Lastly, we perform Brownian Dynamics simulations where each nanoparticle is a spherical bead. This coarsening strategy allows studying the aggregation of a few thousand nanoparticles. Applying this novel procedure, we find three new molecular descriptors, namely, the aggregation free energy and two numerical parameters used to correct the observed deviation from the aggregation kinetics described by the Smoluchowski theory. Ultimately, molecular descriptors can be fed into QSAR models to predict the toxicity of a material knowing its physicochemical properties, enabling safe design strategies.

Multistage and passive cooling process driven by salinity difference.

Space cooling in buildings is anticipated to rise because of an increasing thermal comfort demand worldwide, and this calls for cost-effective and sustainable cooling technologies. We present a proof-of-concept multistage device, where a net cooling capacity and a temperature difference are demonstrated as long as two water solutions at disparate salinity are maintained. Each stage is made of two hydrophilic layers separated by a hydrophobic membrane. An imbalance in water activity in the two layers naturally causes a non-isothermal vapor flux across the membrane without requiring any mechanical ancillaries. One prototype of the device developed a specific cooling capacity of up to 170 W m-2 at a vanishing temperature difference, considering a 3.1 mol/kg calcium chloride solution. To provide perspective, if successfully up-scaled, this concept may help satisfy at least partially the cooling needs in hot, humid regions with naturally available salinity gradients.

Nano-metering of Solvated Biomolecules Or Nanoparticles from Water Self-Diffusivity in Bio-inspired Nanopores.

Taking inspiration from the structure of diatom algae frustules and motivated by the need for new detecting strategies for emerging nanopollutants in water, we analyze the potential of nanoporous silica tablets as metering devices for the concentration of biomolecules or nanoparticles in water. The concept relies on the different diffusion behavior that water molecules exhibit in bulk and nanoconfined conditions, e.g., in nanopores. In this latter situation, the self-diffusion coefficient of water reduces according to the geometry and surface properties of the pore and to the concentration of suspended biomolecules or nanoparticles in the pore, as extensively demonstrated in a previous study. Thus, for a given pore-liquid system, the self-diffusivity of water in nanopores filled with biomolecules or nanoparticles provides an indirect measure of their concentration. Using molecular dynamics and previous results from the literature, we demonstrate the correlation between the self-diffusion coefficient of water in silica nanopores and the concentration of proteins or nanoparticles contained therein. Finally, we estimate the time required for the nanoparticles to fill the nanopores, in order to assess the practical feasibility of the overall nano-metering protocol. Results show that the proposed approach may represent an alternative method for assessing the concentration of some classes of nanopollutants or biomolecules in water.

From GROMACS to LAMMPS: GRO2LAM : A converter for molecular dynamics software.

Atomistic simulations have progressively attracted attention in the study of physical-chemical properties of innovative nanomaterials. GROMACS and LAMMPS are currently the most widespread open-source software for molecular dynamics simulations thanks to their good flexibility, numerous functionalities and responsive community support. Nevertheless, the very different formats adopted for input and output files are limiting the possibility to transfer GROMACS simulations to LAMMPS. In this article, we present GRO2LAM, a modular and open-source Python 2.7 code for rapidly translating input files and parameters from GROMACS to LAMMPS format. The robustness of the tool has been assessed by comparing the simulation results obtained by GROMACS and LAMMPS, after the format conversion by GRO2LAM. Specifically, three nanoscale configurations of interest in both engineering and biomedical fields are studied, namely a carbon nanotube, an iron oxide nanoparticle, and a protein immersed in water. In perspective, GRO2LAM may be the first step to achieve a full interoperability between molecular dynamics software. This would allow to easily exploit their complementary potentialities and post-processing functionalities. Moreover, GRO2LAM could facilitate the cross-check of simulation results, guaranteeing the reproducibility of molecular dynamics models and testing their robustness. Graphical Abstract GRO2LAM, a modular and open-source Python code for rapidly translating input files and parameters from GROMACS to LAMMPS format.

Coffee-based colloids for direct solar absorption.

Despite their promising thermo-physical properties for direct solar absorption, carbon-based nanocolloids present some drawbacks, among which the unpleasant property of being potentially cytotoxic and harmful to the environment. In this work, a sustainable, stable and inexpensive colloid based on coffee is synthesized and its photo-thermal properties investigated. The proposed colloid consists of distilled water, Arabica coffee, glycerol and copper sulphate, which provide enhanced properties along with biocompatibility. The photo-thermal performance of the proposed fluid for direct solar absorption is analysed for different dilutions and compared with that of a traditional flat-plate collector. Tailor-made collectors, opportunely designed and realized via 3D-printing technique, were used for the experimental tests. The results obtained in field conditions, in good agreement with two different proposed models, show similar performance of the volumetric absorption using the proposed coffee-based colloids as compared to the classical systems based on a highly-absorbing surface. These results may encourage further investigations on simple, biocompatible and inexpensive colloids for direct solar absorption.

Multi-scale approach for modeling stability, aggregation, and network formation of nanoparticles suspended in aqueous solutions.

Suspensions of nanoparticles (NPs) in aqueous solutions hold promise in many research fields, including energy applications, water desalination, and nanomedicine. The ability to tune NP interactions, and thereby to modulate the NP self-assembly process, holds the key to rationally synthesize NP suspensions. However, traditional models obtained by coupling the DLVO (Derjaguin, Landau, Verwey, and Overbeek) theory of NP interactions, or suitable modifications of it, with the kinetic theory of colloidal aggregation are inadequate to precisely model NP self-assembly because they neglect hydration forces and discrete-size effects predominant at the nanoscale. By synergistically blending molecular dynamics and stochastic dynamics simulations with continuum theories, we develop a multi-scale (MS) model, which is able to accurately predict suspension stability, timescales for NP aggregation, and macroscopic properties (e.g., the thermal conductivity) of bare and surfactant-coated NP suspensions, in good agreement with the experimental data. Our results enable the formulation of design rules for engineering NP aqueous suspensions in a wide range of applications.

Mesoscopic Moment Equations for Heat Conduction: Characteristic Features and Slow-Fast Mode Decomposition.

In this work, we derive different systems of mesoscopic moment equations for the heat-conduction problem and analyze the basic features that they must hold. We discuss two- and three-equation systems, showing that the resulting mesoscopic equation from two-equation systems is of the telegraphist's type and complies with the Cattaneo equation in the Extended Irreversible Thermodynamics Framework. The solution of the proposed systems is analyzed, and it is shown that it accounts for two modes: a slow diffusive mode, and a fast advective mode. This latter additional mode makes them suitable for heat transfer phenomena on fast time-scales, such as high-frequency pulses and heat transfer in small-scale devices. We finally show that, if proper initial conditions are provided, the advective mode disappears, and the solution of the system tends asymptotically to the transient solution of the classical parabolic heat-conduction equation.