Can a Single Molecule of Water be Completely Isolated Within the Subnano‐Space Inside the Fullerene C60 Cage? A Quantum Chemical Prospective

Based on an experimental observation, it has been controversially suggested in a study (Kurotobi et al., Science 2011 , 33, 613) that a single molecule of water can completely be localized within the subnano‐space inside the fullerene C₆₀ cage and, that neither the H atoms nor the O lone‐pairs are linked, either via hydrogen bonding or through dative bonding, with the interior C‐framework of the C₆₀ cage. To resolve the controversy, electronic structure calculations were performed by using the density functional theory, together with the quantum theory of atoms in molecules, the natural population and bond orbital analyses, and the results were analyzed by using varieties of recommended diagnostics often used to interpret noncovalent interactions. The present results reveal that the mechanically entrapped H₂O molecule is not electronically innocent of the presence of the cage; each H atom of H₂O is weakly O? H???C₆₀ bonded, whereas the O lone‐pairs are O???C₆₀ bonded regardless of the conformations investigated. Exploration of various featured properties suggests that H₂O@C₆₀ may be regarded as a unique system composed of both inter‐ and intramolecular interactions.     

Effect of group velocity dispersion on supercontinuum generation and filamentation in transparent solids

We experimentally investigate the spectral extent and spectral profile of the supercontinuum (SC) generated in transparent solids: barium fluoride, calcium fluoride, and fused silica upon irradiation by intense femtosecond-long pulses of 800, 1,380, and 2,200 nm light. These wavelengths correspond to the normal and anomalous group velocity dispersion (GVD) regimes in fused silica calcium fluoride and barium fluoride. We observe an isolated (anti-Stokes) wing on the blue side most prominently in fused silica but also in CaF₂. The SC conversion efficiency is measured for the long wavelengths used in our experiments. We also present results on filamentation in BaF₂ in the anomalous GVD regime, including visualization of focusing–refocusing events within the crystal; the size of a single filament is also determined. The 15-photon absorption cross section in BaF₂ is deduced to be 6.5 × 10^?190 cm³⁰ W^?15 s^?1.     

Catechol oxidase activity of dinuclear copper(II) complexes of Robson type macrocyclic ligands: Syntheses, X-ray crystal structure, spectroscopic characterization of the adducts and kinetic studies

Five dinuclear copper(II) complexes, [Cu₂L¹(N₃)₂·2H₂O] (1), [Cu₂L²(N₃)₂·2H₂O] (2), [Cu₂L³(N₃)₂·2H₂O] (3), [Cu₂L⁴(N₃)₂·2H₂O] (4) and [Cu₂L⁵(N₃)₂·2H₂O] (5) of Robson type macrocyclic Schiff-base ligands derived from [2 + 2] condensation of 4-methyl-2,6-diformylphenol with 1,3-diaminopropane (H₂L¹), 1,2-diaminoethane (H₂L²), 1,2-diaminopropane (H₂L³), 1,2-diamino-2-methylpropane (H₂L⁴) and 1,2-diaminocyclohexane (H₂L⁵), respectively have been synthesized and characterized. Catecholase activity of those complexes using 3,5-di-tert-butylcatechol as substrate has been investigated in two solvents, methanol and acetonitrile. The role of the solvent and of the steric properties of the macrocyclic ligand of these complexes on their catecholase activity has been examined thoroughly. Acetonitrile is observed to be a better solvent than methanol as far as their catalytic activity is concerned. However, methanol reveals to be a better choice to identify the enzyme–substrate adduct. The investigation also prompted that chelate ring size does affect on the catalytic efficiency: 6-membered ring (as in H₂L¹) exhibits better activity than its 5-membered counterpart (as in H₂L²). The activity of the 5-membered counter parts also depend upon the steric factor. Moreover, the catalytic activity of the complexes is enhanced to a significant extent by increasing the bulkiness of the substituents on the backbone of macrocyclic H₂L² ligands.     

Halogen in materials design: Revealing the nature of hydrogen bonding and other non-covalent interactions in the polymorphic transformations of methylammonium lead tribromide perovskite

Methylammonium lead tribromide (CH₃NH₃PbBr₃) perovskite as a photovoltaic material has attracted a great deal of recent interest. Factors that are important in their application in optoelectronic devices include their fractional contribution of the composition of the materials as well as their microscopic arrangement that is responsible for the formation of well-defined macroscopic structures. CH₃NH₃PbBr₃ assumes different polymorphs (orthorhombic, tetragonal and cubic) depending on the evolution temperature of the bulk material. An understanding of the structure of these compounds will assist in rationalizing how halogen-centered non-covalent interactions play an important role in the rational design of these materials. Density functional theory (DFT) calculations have been performed on polymorphs of CH₃NH₃PbBr₃ to demonstrate that the H atoms on C of the methyl group in CH₃NH₃⁺ entrapped within a PbBr₆^4? perovskite cage are not electronically innocent, as is often contended. We show here that these H atoms are involved in attractive interactions with the surrounding bromides of corner-sharing PbBr₆^4? octahedra of the CH₃NH₃PbBr₃ cage to form Br?H(C) hydrogen bonding interactions. This is analogous to the way the H atoms on N of the NH₃⁺ group in CH₃NH₃⁺ form Br?H(N) hydrogen bonding interactions to stabilize the structure of CH₃NH₃PbBr₃. Both these hydrogen bonding interactions are shown to persist regardless of the nature of the three polymorphic forms of CH₃NH₃PbBr₃. These, together with the Br?C(N) carbon bonding, the Br?N(C) pnictogen bonding, and the Br?Br lump-hole type intermolecular non-covalent interactions identified for the first time in this study, are shown to be collectively responsible for the eventual emergence of the orthorhombic geometry of the CH₃NH₃PbBr₃ system. These conclusions are arrived at from a systematic analysis of the results obtained from combined DFT, Quantum Theory of Atoms in Molecules (QTAIM), and Reduced Density Gradient Non-Covalent Interaction (RDG-NCI) calculations carried out on the three temperature-dependent polymorphic geometries of CH₃NH₃PbBr₃.     

Radical cyclization of exo-methylene furanose derivatives: an expedient approach to the synthesis of chiral tricyclic nucleosides and benzannulated oxepine derivatives

Tributyltin radical mediated cyclization of the glucose derived exo-methylene furanose derivatives 5a-c led to the highly functionalized cis-fused bicyclic ethers 6a-c. The product could subsequently be transformed to the optically active tricyclic nucleoside analogue 8 or oxepine derivative 9.     

Design, Synthesis, and Application of Chiral Nonracemic Lithium Amide Bases in Enantioselective Deprotonation of Epoxides

The reaction of epoxides with chiral nonracemic lithium amide bases, designed and prepared from (R)-phenylglycine, has been studied in detail. A maximum of 80% ee was obtained for conversion of cyclohexene oxide to (S)-2-cyclohexen-1-ol. Enantioselective deprotonation of a variety of other epoxides was studied. A cyclopentanoid core unit for prostaglandin synthesis was synthesized in 97% ee.     

A Scalable Chemical Approach for the Synthesis of a Highly Tolerant and Efficient Oil Absorbent

In the past, bio‐inspired extreme water repellent property has been strategically embedded on commercially available sponges for developing selective oil absorbents. However, most of the reported materials lack physical and chemical durability, limiting their applicability at practically harsh settings. Herein, a stable dispersion of polymeric nanocomplexes was exploited to achieve a chemically reactive coating on the highly compressible melamine foam. A superhydrophobic melamine foam (SMF) was achieved after post‐covalent modification of the reactive coating through 1,4‐conjugate addition reaction at ambient conditions. The durability of the embedded extreme water repellent property in the as‐modified melamine foam has been elaborately demonstrated through exposing it to severe physical manipulations, chemically harsh aqueous media including pH 1, pH 12, surfactant contaminated water, river water, seawater and prolonged UV irradiation. Thus, the highly tolerant SMF was utilized as an efficient oil absorbent wherein oils of varying densities could be selectively recovered from an oil/water interface with high (e.g., 137 g g^?1 for chloroform and 83 g g^?1 for diesel) oil absorption capacity. Moreover, the selective oil absorption capacity of the as‐synthesized material remained unaffected at practically relevant severe chemical and physical settings, and the extreme water repellency of the material remained unaltered even after repetitive (at least 50 cycles) use for oil/water separation.     

Ethnobotanical Uses,Phytochemistry, Toxicology,and Pharmacological Properties of Euphorbia neriifolia Linn. against Infectious Diseases: A Comprehensive Review

Medicinal plants have considerable potential as antimicrobial agents due to the presence of secondary metabolites. This comprehensive overview aims to summarize the classification, morphology, and ethnobotanical uses of Euphorbia neriifolia L. and its derived phytochemicals with the recent updates on the pharmacological properties against emerging infectious diseases, mainly focusing on bacterial, viral, fungal, and parasitic infections. The data were collected from electronic databases, including Google Scholar, PubMed, Semantic Scholar, ScienceDirect, and SpringerLink by utilizing several keywords like ‘Euphorbia neriifolia’, ‘phytoconstituents’, ‘traditional uses’, ‘ethnopharmacological uses’, ‘infectious diseases’, ‘molecular mechanisms’, ‘COVID-19’, ‘bacterial infection’, ‘viral infection’, etc. The results related to the antimicrobial actions of these plant extracts and their derived phytochemicals were carefully reviewed and summarized. Euphol, monohydroxy triterpene, nerifoliol, taraxerol, β-amyrin, glut-5-(10)-en-1-one, neriifolione, and cycloartenol are the leading secondary metabolites reported in phytochemical investigations. These chemicals have been shown to possess a wide spectrum of biological functions. Different extracts of E. neriifolia exerted antimicrobial activities against various pathogens to different extents. Moreover, major phytoconstituents present in this plant, such as quercetin, rutin, friedelin, taraxerol, epitaraxerol, taraxeryl acetate, 3β-friedelanol, 3β-acetoxy friedelane, 3β-simiarenol, afzelin, 24-methylene cycloarenol, ingenol triacetate, and β-amyrin, showed significant antimicrobial activities against various pathogens that are responsible for emerging infectious diseases. This plant and the phytoconstituents, such as flavonoids, monoterpenoids, diterpenoids, triterpenoids, and alkaloids, have been found to have significant antimicrobial properties. The current evidence suggests that they might be used as leads in the development of more effective drugs to treat emerging infectious diseases, including the 2019 coronavirus disease (COVID-19).