Dataset Information

Energy Redistribution Following CO₂ Formation on Cold Amorphous Solid Water.

ABSTRACT: The formation of molecules in and on amorphous solid water (ASW) as it occurs in interstellar space releases appreciable amounts of energy that need to be dissipated to the environment. Here, energy transfer between CO₂ formed within and on the surface of amorphous solid water (ASW) and the surrounding water is studied. Following CO(¹Σ⁺) + O(¹D) recombination the average translational and internal energy of the water molecules increases on the ∼10 ps time scale by 15-25% depending on whether the reaction takes place on the surface or in an internal cavity of ASW. Due to tight coupling between CO₂ and the surrounding water molecules the internal energy exhibits a peak at early times which is present for recombination on the surface but absent for the process inside ASW. Energy transfer to the water molecules is characterized by a rapid ∼10 ps and a considerably slower ∼1 ns component. Within 50 ps a mostly uniform temperature increase of the ASW across the entire surface is found. The results suggest that energy transfer between a molecule formed on and within ASW is efficient and helps to stabilize the reaction products generated.

SUBMITTER: Upadhyay M

PROVIDER: S-EPMC8861491 | biostudies-literature | 2021

REPOSITORIES: biostudies-literature

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Publications

Energy Redistribution Following CO2 Formation on Cold Amorphous Solid Water.

Upadhyay Meenu M Meuwly Markus M

Frontiers in chemistry 20220208

The formation of molecules in and on amorphous solid water (ASW) as it occurs in interstellar space releases appreciable amounts of energy that need to be dissipated to the environment. Here, energy transfer between CO2 formed within and on the surface of amorphous solid water (ASW) and the surrounding water is studied. Following CO(1Σ+) + O(1D) recombination the average translational and internal energy of the water molecules increases on the ∼ 10 ps ...[more]

PMID: 35211461

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Project description:Many different molecular species have been observed in the interstellar medium. These range from simple diatomic species to saturated organic molecules with several carbon atoms. The latter molecules are assumed to be formed predominantely on the surface of interstellar dust grains. All surface reactions that can proceed under the low interstellar temperatures are exothermic. Their exothermicity can be as high as a few electron volts, which is considerable compared to the thermal energy of the molecules at 10 K. It is postulated that this exothermicity can be used for the desorption of reaction products from the grain. In previous studies, we have shown that translational excitation can lead to desorption, whereas vibrational and rotational excitations are much less efficient in the desorption of surface products. Vibrational excitation is however much more likely upon bond formation than translational excitation. The present study follows energy dissipation upon translational, vibrational, or rotational excitation of admolecules on a surface and its conversion, or lack thereof, to different energy contributions. To this end, thousands of molecular dynamics simulations were performed with an admolecule on top of a surface that received a fixed amount of energy, vibrational, rotational, or translational. Three different surface species have been considered, CO2, H2O, and CH4, spanning a range in binding energies, the number of internal degrees of freedom, and molecular weights. A fast exchange of energy between vibrational stretches is observed, but only very limited exchange to rotational or translation excitation has been found. For the dissipation of energy to the surface, excitation of the surface-admolecule bond is critical. Astrochemical models often assume instantaneous equipartition of energy after a reaction process to estimate the amount of available energy for chemical desorption. Based on the present study, we conclude that this assumption is not justified.

Project description:Spray drying is widely used in the manufacturing of amorphous solid dispersion (ASD) systems due to its fast drying rate, enabling kinetic trapping of the drug in amorphous form. Spray-drying conditions, such as solvent composition, can have a profound impact on the properties of spray-dried dispersions. In this study, the phase behavior of spray-dried dispersions from methanol and methanol-water mixtures was assessed using ritonavir and copovidone [poly(vinylpyrrolidone-co-vinyl acetate) (PVPVA)] as dispersion components. The resultant ASDs were characterized using differential scanning calorimetry (DSC), fluorescence spectroscopy, X-ray photoelectron spectroscopy (XPS), as well as surface-normalized dissolution rate (SNDR) measurements. Quaternary phase diagrams were calculated using a four-component Flory-Huggins model. It was found that the addition of water to the solvent system can lead to phase separation during the spray-drying process. A 10:90 H2O/MeOH solvent system caused a minor extent of phase separation. Phase heterogeneity in the 50 and 75% drug loading ASDs prepared from this spray solvent can be detected using DSC but not with other techniques used. The 25% drug loading system did not show phase heterogeneity in solid-state characterization but exhibited a compromised dissolution rate compared to that of the miscible ASD prepared from H2O-free solvent. This is possibly due to the formation of slow-releasing drug-rich phases upon phase separation. ASDs prepared with a 60:40 H2O/MeOH solvent mixture showed phase heterogeneity with all analytical methods used. The surface composition of dispersion particles as measured by fluorescence spectroscopy and XPS showed good agreement, suggesting surface drug enrichment of the spray-dried ASD particles prepared from this solvent system. Calculated phase diagrams and drying trajectories were consistent with experimental observations, suggesting that small variations in solvent composition may cause significant changes in ASD phase behavior during drying. These findings should aid in spray-drying process development for ASD manufacturing and can be applied broadly to assess the risk of phase separation for spray-drying systems using mixed organic solvents or other solvent-based processes.

Dataset Information

Energy Redistribution Following CO₂ Formation on Cold Amorphous Solid Water.

Publications

Energy Redistribution Following CO<sub>2</sub> Formation on Cold Amorphous Solid Water.

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