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.     

Stereoselective synthesis of hydroxy stilbenoids and styrenes by atom-efficient olefination with thiophthalides

The synthesis of stilbenoids and styryl carboxylic acids is accomplished with high E-stereoselectivity by olefination of aldehydes with thiophthalides under basic conditions. The olefination is highly atom-efficient as it only loses elemental sulfur during the reaction. This olefination, in conjunction with retro Kolbe-Schmitt reaction, allows facile synthesis of E-hydroxystilbenoids with minimal employment of protecting groups. This study also discloses two important findings: formation of i) 4-methylsulfanyl isocoumarins and ii) an 2-arylindenone.     

Spontaneous Formation of Biocompatible Vesicles in Aqueous Mixtures of Amino Acid‐Based Cationic Surfactants and SDS/SDBS

The spontaneous formation of vesicles by six amino acid‐based cationic surfactants and two anionic surfactants (sodium dodecylbenzene sulfonate (SDBS) and sodium dodecyl sulfate (SDS)) is reported. The head‐group structure of the cationic surfactants is minutely altered to understand their effect on vesicle formation. To establish the regulatory role of the aromatic group in self‐aggregation, both aliphatic and aromatic side‐chain‐substituted amino acid‐based cationic surfactants are used. The presence of aromaticity in any one of the constituents favors the formation of vesicles by cationic/anionic surfactant mixtures. The formation of vesicles is primarily dependent on the balance between the hydrophobicity and hydrophilicity of both cationic and anionic surfactants. Vesicle formation is characterized by surface tension, fluorescence anisotropy, transmission electron microscopy, dynamic light scattering, and phase diagrams. These vesicles are thermally stable up to 65 °C, determined by temperature‐dependent fluorescence anisotropy. According to the MTT assay, these catanionic vesicles are nontoxic to NIH3T3 cells, thus indicating their wider applicability as delivery vehicles to cells. Among the six cationic surfactants examined, tryptophan‐ and tyrosine‐based surfactants have the ability to reduce HAuCl₄ to gold nanoparticles (GNPs), which is utilized to obtain in‐situ‐synthesized GNPs entrapped in vesicles without the need for any external reducing agent.     

DFT-B3LYP, NPA-, and QTAIM-based study of the physical properties of [M(II)(H2O)2(15-crown-5)] (M = Mn, Fe, Co, Ni, Cu, Zn) complexes

A density functional theory study of the structure of the title compounds with the divalent metal ions in their high-spin ground state, obtained using B3LYP/6-311++G(d,p) in vacuo and in aqueous solution simulated using a polarized continuum medium, is reported for the first time. The modeling reproduces the pseudo pentagonal bipyramidal crystallographic structures very well, including some asymmetry in the equatorial bonds lengths to the crown ether O donors. The very marked asymmetry in the Ni(2+) structure due to a Jahn-Teller distortion of a d(8) system in a D(5h) ligand field is also well reproduced. The gas phase binding energies of the complexes follow the order Mn(2+) < Fe(2+) < Co(2+) < Ni(2+) < Cu(2+) > Zn(2+), in precise agreement with the Irving-William series. Both the NPA and Bader charges show there is ligand-to-metal charge transfer; however, the values obtained from the NPA procedure, unlike those obtained from Bader's quantum theory of molecules approach, do not correlate with the electronegativity of the metal ions, the stabilization energies of the solvated complexes or the ionic radii of the metal ions, and so appear to be less reliable. The nature of the bonding between the ligands and the metal ions has been explored using the topological properties of the electron charge density. The metal-ligand bond distances were found to be exponentially correlated with the electron charge density, its Laplacian, and with its curvature in the direction of the bond path at M-O bond critical points. While the bonding with coordinated H(2)O is predominantly ionic, that to the crown ether donor atoms has some covalent character the extent of which increases across the first transition series. The delocalization indices of M-O bonds in these complexes correlate reasonably well with the electron density and its Laplacian at the bond critical points; this therefore provides a rapid and computationally very efficient way of determining these properties, from which insight into the nature of the bonding can be obtained, obviating the need for time-consuming integration over atomic basins.     

Amyloid‐Like Fibrillogenesis through Supramolecular Helix‐Mediated Self‐Assembly of Tetrapeptides Containing Non‐Coded α‐Aminoisobutyric Acid (Aib) and 3‐Aminobenzoic Acid (m‐ABA)

Single‐crystal X‐ray diffraction studies of two terminally protected tetrapeptides Boc‐Ile‐Aib‐Val‐m‐ABA‐OMe ( I ) and Boc‐Ile‐Aib‐Phe‐m‐ABA‐OMe ( II ) (Aib=α‐aminoisobutyric acid; m‐ABA=meta‐aminobenzoic acid) reveal that they form continuous H‐bonded helices through the association of double‐bend (type III and I) building blocks. NMR Studies support the existence of the double‐bend (type III and I) structures of the peptides in solution also. Field emission scanning electron‐microscopic (FE‐SEM) and high‐resolution transmission electron‐microscopic (HR‐TEM) images of the peptides exhibit amyloid‐like fibrils in the solid state. The Congo red‐stained fibrils of peptide I and II , observed between crossed polarizers, show green‐gold birefringence, a characteristic of amyloid fibrils.     

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.     

Superconductivity and thermal properties of sulphur doped FeTe with effect of oxygen post annealing

Here, we report the synthesis and characterization of sulphur-substituted iron telluride i.e. FeTe_1?xS_x; (x = 0–30 %) system and study the impact of low temperature oxygen (O₂) annealing as well. Rietveld analysis of room temperature X-ray diffraction (XRD) patterns shows that all the compounds are crystallized in a tetragonal structure (space group P4/nmm) and no secondary phases are observed. Lattice constants are decreased with increasing S concentration. The parent compound of the system i.e. FeTe does not exhibit superconductivity but shows an anomaly in the resistivity measurement at around 78 K, which corresponds to a structural phase transition. Heat capacity C_p(T) measurement also confirms the structural phase transition of FeTe compound. Superconductivity appears by S substitution; the onset of superconducting transition temperature is about 8 K for FeTe_0.75S_0.25 sample. Thermoelectric power measurements S(T) also shows the superconducting transition at around 7 K for FeTe_0.75S_0.25 sample. The upper critical fields H_c2(10%), H_c2(50%) and H_c2(90%) are estimated to be 400, 650 and 900 kOe respectively at 0 K by applying Ginzburg Landau (GL) equation. Interestingly, superconducting volume fraction is increased with low temperature (200 °C) O₂ annealing at normal pressure. Detailed investigations related to structural (XRD), transport [S(T), R(T)H], magnetization (AC and DC susceptibility) and thermal [C_p(T)] measurements for FeTe_1?xS:O₂ system are presented and discussed.     

Design and synthesis of azobenzene template based sulfonamide for capture of HCAII: dependence of efficiency on E–Z geometry

We report the synthesis of azobenzene template based sulfonamides 1 and 2 for capture of Human Carbonic Anhydrase II (HCAII). Out of these, 1 showed successful capturing of the protein, only when it is photo-isomerized to the Z form thus demonstrating the importance of spatial proximity of the reactive and selective functionalities.