Dataset Information

Probing the energetics of organic-nanoparticle interactions of ethanol on calcite.

ABSTRACT: Knowing the nature of interactions between small organic molecules and surfaces of nanoparticles (NP) is crucial for fundamental understanding of natural phenomena and engineering processes. Herein, we report direct adsorption enthalpy measurement of ethanol on a series of calcite nanocrystals, with the aim of mimicking organic-NP interactions in various environments. The energetics suggests a spectrum of adsorption events as a function of coverage: strongest initial chemisorption on active sites on fresh calcite surfaces, followed by major chemical binding to form an ethanol monolayer and, subsequently, very weak, near-zero energy, physisorption. These thermochemical observations directly support a structure where the ethanol monolayer is bonded to the calcite surface through its polar hydroxyl group, leaving the hydrophobic ends of the ethanol molecules to interact only weakly with the next layer of adsorbing ethanol and resulting in a spatial gap with low ethanol density between the monolayer and subsequent added ethanol molecules, as predicted by molecular dynamics and density functional calculations. Such an ordered assembly of ethanol on calcite NP is analogous to, although less strongly bonded than, a capping layer of organics intentionally introduced during NP synthesis, and suggests a continuous variation of surface structure depending on molecular chemistry, ranging from largely disordered surface layers to ordered layers that nevertheless are mobile and can rearrange or be displaced by other molecules to strongly bonded immobile organic capping layers. These differences in surface structure will affect chemical reactions, including the further nucleation and growth of nanocrystals on organic ligand-capped surfaces.

SUBMITTER: Wu D

PROVIDER: S-EPMC4418924 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Similar Datasets

Project description:Platelets, one of the most sensitive blood cells, can be activated by a range of external and internal stimuli including physical, chemical, physiological, and/or non-physiological agents. Platelets need to respond promptly during injury to maintain blood hemostasis. The time profile of platelet aggregation is very complex, especially in the presence of the agonist adenosine 5'-diphosphate (ADP), and it is difficult to probe such complexity using traditional linear dose response models. In the present study, we explored functional analysis techniques to characterize the pattern of platelet aggregation over time in response to nanoparticle induced perturbations. This has obviated the need to represent the pattern of aggregation by a single summary measure and allowed us to treat the entire aggregation profile over time, as the response. The modeling was performed in a flexible manner, without any imposition of shape restrictions on the curve, allowing smooth platelet aggregation over time. The use of a probabilistic framework not only allowed statistical prediction and inference of the aggregation signatures, but also provided a novel method for the estimation of higher order derivatives of the curve, thereby allowing plausible estimation of the extent and rate of platelet aggregation kinetics over time. In the present study, we focused on the estimated first derivative of the curve, obtained from the platelet optical aggregometric profile over time and used it to discern the underlying kinetics as well as to study the effects of ADP dosage and perturbation with gold nanoparticles. In addition, our method allowed the quantification of the extent of inter-individual signature variations. Our findings indicated several hidden features and showed a mixture of zero and first order kinetics interrupted by a metastable zero order ADP dose dependent process. In addition, we showed that the two first order kinetic constants were ADP dependent. However, we were able to perturb the overall kinetic pattern using gold nanoparticles, which resulted in autocatalytic aggregation with a higher aggregate mass and which facilitated the aggregation rate.

Dataset Information

Probing the energetics of organic-nanoparticle interactions of ethanol on calcite.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets