The mechanism and enantioselectivity of the organocatalytic Diels-Alder reaction were computationally investigated by density functional theory at the B3LYP/6-31G(d) level of theory. The uncatalyzed Diels-Alder reaction was also studied to explore the effect of the organocatalyst on this reaction in terms of energetics, selectivity, and mechanism. The catalyzed reaction showed improved endo/exo selectivity, and the free energy of activation was significantly lowered in the presence of the catalyst. Both uncatalyzed and catalyzed reactions exhibited concerted asynchronous reaction mechanism with the degree of asynchronicity being more evident in the presence of the catalyst. The Corey's experimentally derived predictive selection rules for the outcome of the organocatalytic Diels-Alder reaction were also theoretically analyzed, and an excellent agreement was found between experiment and theory.
In this study, structural, electronic, optical, thermoelectric, and thermodynamics properties of vacancy-ordered double perovskites Rb2 XCl6 (X = Se, Ti) were explored theoretically. The results revealed that Rb2SeCl6 and Rb2 TiCl6 are indirect band gap (Eg ) semiconductors with Eg values of 2.95 eV, and 2.84 eV respectively. The calculated properties (phonons, elastic constant, Poisson's ratio, and Pugh's ratio) revealed that both materials are dynamically and chemically stable and can exhibit brittle (Rb2 SeCl6 ) and ductile (Rb2 TiCl6 ) nature. From the analysis of optical parameters, it was noticed that the refractive index of the materials has a value of 1.5-2.0 where light absorption was found from the visible to the ultraviolet region. The thermoelectric properties determined by using the BoltzTrap code demonstrated that at room temperature, the Figure of merit (ZT) was found to be 0.74 and 0.76 for Rb2 SeCl6 and Rb2 TiCl6 , respectively. Despite a moderate value of ZT in such materials, further studies might explore effective methods for tuning the electronic band gap and improving the thermoelectric response of the material for practical energy production applications.
In this study, the enantioselectivity of β-cyclodextrin and its derivatives towards propranolol enantiomers are investigated by molecular dynamic (MD) simulations. β-cyclodextrin (β-CD) have previously been shown to be able to recognize propranolol (PRP) enantiomers. To improve upon the enantioselectivity of β-cyclodextrin, we propose the use of an ionic-liquid-modified-β-cyclodextrin (β-CD-IL). β-CD-IL was found to be able to complex R and S propranolol enantiomers with differing binding energies. The molecular docking study reveals that the ionic liquid chain attached to the β-CD molecule has significant interaction with propranolol. The formation of the most stable complex occurred between (S)-β-CD-IL and (S)-propranolol with an energy of -5.80 kcal/mol. This is attributed to the formation of a hydrogen bond between the oxygen of the propranolol and the hydrogen on the primary rim of the (S)-β-CD-IL cavity. This interaction is not detected in other complexes. The root mean-squared fluctuation (RMSF) value indicates that the NH group is the most flexible molecular fragment, followed by the aromatic group. Also of note, the formation of a complex between pristine β-CD and (S)-propranolol is the least favorable.