記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AIP Publishing  

We conducted molecular dynamics (MD) simulations in a binary Lennard-Jones system as a model system for molecular solutions and investigated the mechanism of liquid-liquid phase separation (LLPS), which has recently been recognized as a fundamental step in crystallization and organelle formation. Our simulation results showed that LLPS behavior varied drastically with the size ratio of solute to solvent molecules. Interestingly, increasing the size ratio can either facilitate or inhibit LLPS, depending on the combination of interaction strengths. We demonstrated that the unique behavior observed in MD simulation could be reasonably explained by the free energy barrier height calculated using our thermodynamic model based on the classical nucleation theory. Our model proved that the molecular size determines the change in number of interaction pairs through LLPS. Varying the size ratio changes the net number of solute-solvent and solvent-solvent interaction pairs that are either broken or newly generated per solute-solute pair generation, thereby inducing a complicated trend in LLPS depending on the interaction parameters. As smaller molecules have more interaction pairs per unit volume, their contribution is more dominant in the promotion of LLPS. Consequently, as the size ratio of the solute to the solvent increased, the LLPS mode changed from solute-related interaction-driven to solvent-related interaction-driven.

DOI： 10.1063/5.0190119

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：NATL ACAD SCIENCES  

Flexible metal-organic frameworks (MOFs) exhibit an adsorption-induced structural transition known as "gate opening" or "breathing," resulting in an S-shaped adsorption isotherm. This unique feature of flexible MOFs offers significant advantages, such as a large working capacity, high selectivity, and intrinsic thermal management capability, positioning them as crucial candidates for revolutionizing adsorption separation processes. Therefore, the interest in the industrial applications of flexible MOFs is increasing, and the adsorption engineering for flexible MOFs is becoming important. However, despite the establishment of the theoretical background for adsorption induced structural transitions, no theoretical equation is available to describe S-shaped adsorption isotherms of flexible MOFs. Researchers rely on various empirical equations for process simulations that can lead to unreliable outcomes or may overlook insights into improving material performance owing to parameters without physical meaning. In this study, we derive a theoretical equation based on statistical mechanics that could be a standard for the structural transition type adsorption isotherms, as the Langmuir equation represents type I isotherms. The versatility of the derived equation is shown through four examples of flexible MOFs that exhibit gate opening and breathing. The consistency of the formula with existing theories, including the osmotic free energy analysis and intrinsic thermal management capabilities, is also discussed. The developed theoretical equation may lead to more reliable and insightful outcomes in adsorption separation processes, further advancing the direction of industrial applications of flexible MOFs.

DOI： 10.1073/pnas.2305573120

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

The nucleation process, which is the initial step in particle synthesis, determines the properties of the resultant particles. Although recent studies have observed various nucleation pathways, the physical factors that determine these pathways have not been fully elucidated. Herein, we conducted molecular dynamics simulations in a binary Lennard-Jones system as a model solution and found that the nucleation pathway can be classified into four types depending on microscopic interactions. The key parameters are (1) the strength of the solute-solute interaction and (2) the difference between the strengths of the like-pair and unlike-pair interactions. The increment of the former alters the nucleation mechanism from a two-step to a one-step pathway, whereas that of the latter causes quick assembly of solutes. Moreover, we developed a thermodynamic model based on the formation of core-shell nuclei to calculate the free energy landscapes. Our model successfully described the pathway observed in the simulations and demonstrated that the two parameters, (1) and (2), define the degree of supercooling and supersaturation, respectively. Thus, our model interpreted the microscopic insights from a macroscopic point of view. Because the only inputs required for our model are the interaction parameters, our model can a priori predict the nucleation pathway.

DOI： 10.1021/acs.jpcb.2c08893

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