Hegoi Manzano

Confined water dissociation in microporous defective silicates: mechanism, dipole distribution, and impact on substrate properties.

Interest in microporous materials has risen in recent years, as they offer a confined environment that is optimal to enhance chemical reactions. Calcium silicate hydrate (C-S-H) gel, the main component of cement, presents a layered structure with sub-nanometer-size disordered pores filled with water and cations. The size of the pores and the hydrophilicity of the environment make C-S-H gel an excellent system to study the possibility of confined water reactions. To investigate it, we have performed molecular dynamics simulations using the ReaxFF force field. The results show that water does dissociate to form hydroxyl groups. We have analyzed the water dissociation mechanism, as well as the changes in the structure and water affinity of the C-S-H matrix and water polarization, comparing the results with the behavior of water in a defective zeolite. Finally, we establish a relationship between water dissociation in C-S-H gel and the increase of hardness due to a transformation from a two- to a three-dimensional structure.

Hydration of calcium oxide surface predicted by reactive force field molecular dynamics.

In this work, we present the parametrization of Ca-O/H interactions within the reactive force field ReaxFF, and its application to study the hydration of calcium oxide surface. The force field has been fitted using density functional theory calculations on gas phase calcium-water clusters, calcium oxide bulk and surface properties, calcium hydroxide, bcc and fcc Ca, and proton transfer reactions in the presence of calcium. Then, the reactive force field has been used to study the hydration of the calcium oxide {001} surface with different water contents. Calcium oxide is used as a catalyzer in many applications such as CO(2) sequestration and biodiesel production, and the degree of surface hydroxylation is a key factor in its catalytic performance. The results show that the water dissociates very fast on CaO {001} bare surfaces without any defect or vacancy. The surface structure is maintained up to a certain amount of water, after which the surface undergoes a structural rearrangement, becoming a disordered calcium hydroxyl layer. This transformation is the most probable reason for the CaO catalytic activity decrease.

Aluminum Incorporation to Dreierketten Silicate Chains

This work explores, from a theoretical viewpoint, the aluminum incorporation into silicate chains with dreierketten conformation relevant in the cementitious calcium-silicate-hydrate (C-S-H) gel and in other minerals, such as wollastonite and hillebrandite. To this end, we have investigated by means of ab initio calculations both the stability and the formation of aluminosilicate chains. Our results show that only certain aluminosilicate chains are stable, namely, those whose tetrahedra length m obey the m = 3n-1 rule with n = 1, 2, 3, ..., in agreement with experiments. Moreover, our detailed analyses explain why A1 ions prefer the bridging sites and introduce new insights on the growth process.

Do cement nanotubes exist

Using atomistic simulations, this work indicates that cement nanotubes can exist. The chemically compatible nanotubes are constructed from the two main minerals in ordinary Portland cement pastes, namely calcium hydroxide and a calcium silicate hydrate called tobermorite. These results show that such nanotubes are stable and have outstanding mechanical properties, unique characteristics that make them ideally suitable for nanoscale reinforcements of cements.

Insight on Tricalcium Silicate Hydration and Dissolution Mechanism from Molecular Simulations.

Hydration of mineral surfaces, a critical process for many technological applications, encompasses multiple coupled chemical reactions and topological changes, challenging both experimental characterization and computational modeling. In this work, we used reactive force field simulations to understand the surface properties, hydration, and dissolution of a model mineral, tricalcium silicate. We show that the computed static quantities, i.e., surface energies and water adsorption energies, do not provide useful insight into predict mineral hydration because they do not account for major structural changes at the interface when dynamic effects are included. Upon hydration, hydrogen atoms from dissociated water molecules penetrate into the crystal, forming a disordered calcium silicate hydrate layer that is similar for most of the surfaces despite wide-ranging static properties. Furthermore, the dynamic picture of hydration reveals the hidden role of surface topology, which can lead to unexpected water tessellation that stabilizes the surface against dissolution.

Rational Design of Advanced Photosensitizers Based on Orthogonal BODIPY Dimers to Finely Modulate Singlet Oxygen Generation

The synthesis, photophysical characterization, and modeling of a new library of halogen-free photosensitizers (PS) based on orthogonal boron dipyrromethene (BODIPY) dimers are reported. Herein we establish key structural factors in order to enhance singlet oxygen generation by judiciously choosing the substitution patterns according to key electronic effects and synthetic accessibility factors. The photosensitization mechanism of orthogonal BODIPY dimers is demonstrated to be strongly related to their intrinsic intramolecular charge transfer (ICT) character through the spin-orbit charge-transfer intersystem crossing (SOCT-ISC) mechanism. Thus, singlet oxygen generation can be effectively modulated through the solvent polarity and the presence of electron-donating or withdrawing groups in one of the BODIPY units. The photodynamic therapy (PDT) activity is demonstrated by in vitro experiments, showing that selected photosensitizers are efficiently internalized into HeLa cells, exhibiting low dark toxicity and high phototoxicity, even at low PS concentration (0.05-5×10-6  m).

AcetylacetonateBODIPY-Biscyclometalated Iridium(III) Complexes: Effective Strategy towards Smarter Fluorescent Photosensitizer Agents

Biscyclometalated IrIII complexes involving boron-dipyrromethene (BODIPY)-based ancillary ligands, where the BODIPY unit is grafted to different chelating cores (acetylacetonate for Ir-1 and Ir-2, and bipyridine for Ir-3) by the BODIPY meso position, have been synthesized and characterized. Complexes with the BODIPY moiety directly grafted to acetylacetonate (Ir-1 and Ir-2) exhibit higher absorption coefficients (ϵ≈4.46×104  m-1  cm-1 and 3.38×104  m-1  cm-1 at 517 nm and 594 nm, respectively), higher moderate fluorescence emission (φfl ≈0.08 and 0.22 at 528 nm and 652 nm, respectively) and, in particular, more efficient singlet oxygen generation upon visible-light irradiation (φΔ ≈0.86 and 0.59, respectively) than that exhibited by Ir-3 (φΔ ≈0.51, but only under UV light). Phosphorescence emission, nanosecond time-resolved transient absorption, and DFT calculations suggest that BODIPY-localized long-lived 3 IL states are populated for Ir-1 and Ir-2. In vitro photodynamic therapy (PDT) activity studied for Ir-1 and Ir-2 in HeLa cells shows that such complexes are efficiently internalized into the cells, exhibiting low dark- and high photocytoxicity, even at significantly low complex concentration, making them potentially suitable as theranostic agents.

Water Isotherms, Shrinkage and Creep of Cement Paste: Hypotheses, Models and Experiments

Cement paste has a complex mesoscale structure, and small changes in its pore network potentially causing large variation in measurements such as the water isotherm (also nitrogen). We deconvolute the water isotherm with the help of advanced computational techniques, hypotheses, and a re-examination of published data. The pore system is divided into four different categories, each containing water with its own physical properties. By viewing the highly interdependent roles of water in each of the pore categories as a system, new insights are gained regarding possible mechanisms that control drying shrinkage and creep, and experimental strategies for verification.

Interfacial Connection Mechanisms in Calcium–Silicate–Hydrates/Polymer Nanocomposites: A Molecular Dynamics Study

Properties of organic/inorganic composites can be highly dependent on the interfacial connections. In this work, molecular dynamics, using pair-potential-based force fields, was employed to investigate the structure, dynamics, and stability of interfacial connections between calcium-silicate-hydrates (C-S-H) and organic functional groups of three different polymer species. The calculation results suggest that the affinity between C-S-H and polymers is influenced by the polarity of the functional groups and the diffusivity and aggregation tendency of the polymers. In the interfaces, the calcium counterions from C-S-H act as the coordination atoms in bridging the double-bonded oxygen atoms in the carboxyl groups (-COOH), and the Ca-O connection plays a dominant role in binding poly(acrylic acid) (PAA) due to the high bond strength defined by time-correlated function. The defective calcium-silicate chains provide significant numbers of nonbridging oxygen sites to accept H-bonds from -COOH groups. As compared with PAA, the interfacial interactions are much weaker between C-S-H and poly(vinyl alcohol) (PVA) or poly(ethylene glycol) (PEG). Predominate percentage of the -OH groups in the PVA form H-bonds with inter- and intramolecule, which results in the polymer intertwining and reduces the probability of H-bond connections between PVA and C-S-H. On the other hand, the inert functional groups (C-O-C) in poly(ethylene glycol) (PEG) make this polymer exhibit unfolded configurations and move freely with little restrictions. The interaction mechanisms interpreted in this organic-inorganic interface can give fundamental insights into the polymer modification of C-S-H and further implications to improving cement-based materials from the genetic level.

Preparation, Photophysical Characterization, and Modeling of LDS722/Laponite 2D-Ordered Hybrid Films

A novel hybrid material with promising optical properties for nonlinear optical applications is presented, as formed by LDS 722 organic dye confined in Laponite clay. Thin films of the hybrid material with different dye loadings have been prepared. The film thickness, the dye and water content, and the clay swelling due to guest molecule incorporation have been characterized. Then, the photophysical properties of the thin films have been studied in detail using experimental methods and molecular simulation. As the dye load increases, the hybrid films present a hypsochromic shift in absorption and a bathochromic shift in emission. The former is attributed to the increasing strength of solvation of the dye donor group, while the latter is ascribed to a switch from an intramolecular to an intermolecular charge-transfer process as the dye load increases. The LDS 722 molecules are preferentially oriented in the host clay almost in parallel to the platelet surfaces, inducing macroscopic order that makes the material responsive to polarized light.