Pb,Sr and Ba calix[6]arene hexacarboxylic acid octahedral complexation: a dramatic effect of dealkylation

Calix[6]arene hexacarboxylic acid binds instantly and with low symmetry to Pb, Sr and Ba. Later a highly symmetric up-down alternating conformation emerges. The solution structures are identical to their p-tert-butylcalix[6]arene hexacarboxylic acid counterparts. With either receptor, an octahedral cage is formed around the metal. The transformation from low to high symmetry however proceeds at significantly faster rates for the de-t-butylated host.     

A rapid,highly efficient,and general protocol for the synthesis of functionalized triarylmethanes: a straightforward access for the synthesis of (−)-tatarinoid C

A rapid, efficient, and convenient synthesis of functionalized triarylmethane is described by the Friedel–Crafts alkylation of methoxybenzenes with a variety of aldehydes in the presence of BF₃·OEt₂. The generality of the method is demonstrated by screening a variety of di- or tri-substituted arenes as well as substituted aromatic, heteroaromatic, and aliphatic aldehydes. (−)-Tatarinoid C is synthesized in a single step following the same protocol.     

Self‐emulsion polymerization of amphiphilic monomers—a green route to synthesis of polymeric nanoscaffolds

Self‐emulsion polymerization (SEP), a green route developed by us for the polymerization of amphiphilic monomers, does not require any emulsifier or an organic solvent except that the water‐soluble initiators such as 2,2′‐azobis[2‐(2‐imidazolin‐2‐yl)propane]dihydrochloride (VA‐044) and potassium persulfate (KPS) are only used. We report here the polymer nanoscaffolds from a number of amphiphilic monomers, which can be used for in situ encapsulation of a variety of nanoparticles. As a demonstration of the efficacy of these nanoscaffolds, the synthesis of a biocompatible hybrid nanoparticle (nanohybrid), prepared by encapsulating Fe₃O₄ magnetic nanoparticle (Fe₃O₄ MNPs) in poly(2‐hydroxyethyl methacrylate) in water, for MRI application is presented. The nanohybrid prepared following the SEP in the form of an emulsion does not involve the use of any stabilizing agent, crosslinker, polymeric emulsifier, or surfactant. This water‐soluble, spherical, and stable nanohybrid containing Fe₃O₄ MNPs of average size 10 ± 2 nm has a zeta potential value of ?41.89 mV under physiological conditions. Magnetic measurement confirmed that the nanohybrid shows typical magnetic behavior having a saturation magnetization (Ms) value of 32.3 emu/g and a transverse relaxivity (r2) value of 29.97 mM^?1 s^?1, which signifies that it can be used as a T2 contrast agent in MRI. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019     

Total and Semi‐Syntheses of Antimicrobial Thuggacin Derivatives

The total and semi‐synthesis of 13 new macrolactones derived from thuggacin, which is a secondary metabolite from the myxobacterium Sorangium cellulosum, are reported. The thuggacins have attracted much attention due to their strong antibacterial activity, particularly towards Mycobacterium tuberculosis. This study focuses on 1) thuggacin derivatives that cannot equilibrate by transacylation between the three natural thuggacins A–C, 2) the roles of the thiazole ring, and 3) the hexyl side chain at C2. Semi‐synthetic O‐methylation at C17 suppressed the transacylations without a substantial loss of antibacterial activity. Exchanging the C17–C25 side chain for simplified hydrophobic chains led to complete loss of antibacterial activity. Exchange of the thiazole by an oxazole ring or removal of the hexyl side chain at C2 had no substantial effect on the biological properties.     

An experimental investigation on heat transfer enhancement in circular jet impingement on hot surfaces by using Al2O3/water nano-fluids and aqueous high-alcohol surfactant solution

The present article reports the heat transfer characteristics of a vertical stainless steel foil of 0.15 mm thickness (SS304) by circular impinging jets of various fluids such as pure water, nano-fluids (Al₂O₃-water, ф = 0.15%, 0.6%), and aqueous high-alcohol surfactant (HAS, i.e., 2-ethyl-hexanol, 100–400 ppm) studied using an infrared thermal imaging camera (A655sc, FLIR System). The enhancement in the heat transfer rates for Al₂O₃-water nano-fluids with ф = 0.15%, ф = 0.60%, and aqueous surfactant solution (150ppm) is found to be 140%, 207%, and 117% higher compared to pure water results, respectively. The surface characteristics of the foil after jet impingement by various fluids are also studied using scanning electron microscopy (SEM), energy dispersive spectrometer (EDS), and surface wettability.     

Ultrafast Excited State Relaxation Dynamics of New Fuchsine- a Triphenylmethane Derivative Dye

An all-inclusive investigation of the ultrafast excited state relaxation dynamics of a triphenylmethane derivative molecule, New Fuchsine (NF), using a combined approach of density functional theory (DFT), femtosecond transient absorption spectroscopy (fs-TAS), and photoluminescence spectroscopy is presented in this work. The DFT calculations confirmed the formation of twisted molecular structure in the excited state of NF in ethanol solution with bond rotation of ≈86°. TAS measurements of NF solution exhibited ultrafast ground state-recovery pathway via a conical intersection confirming an ultrafast structural reorientation. On the contrary, TAS measurements of NF thin-film exhibited a longer excited-state lifetime suggesting a hindered molecular twisted state formed as an intermediate step. Photophysical kinetic models are proposed to globally fit the fs-TAS data establishing the twisted intramolecular charge transfer (TICT) state mediated ground state recovery for NF in solution and thin film, respectively. Temperature-dependent photoluminescence study of NF film provided a clear insight into the effect of rotational motion of phenyl rings in NF molecules over the TICT mediated emission.     

Transition Metal-Catalyzed Hydroalkoxylation of Alkynes: An Overview

Oxygen-bearing motifs, mainly the congener heterocycles are ubiquitous due to their presence in various natural products and bioactive scaffolds. Although in literature, several strategies have been developed for their synthesis, hydroalkoxylation of alkynes has come forward as a method of choice and has been used extensively. In particular, hydroalkoxylation of alkynes has gained enormous attention from the synthetic community due to the rapid access to a very useful and reactive synthetic intermediate like ‘enol ether’. Furthermore, to manifold the utility of these methods, reports have been developed elaborating the generation of ‘enol ether’ using hydroalkoxylation and their usage in various reactions in cascade or tandem manner. This review focuses on recent development on the hydroalkoxylation of alkynes for the synthesis of oxygen-containing entities.     

Synthesis and characterization of eumelanin‐inspired poly(indoylenearylenevinylene)s and poly(indoylenearyleneethynylene)s

Four novel conjugated polymers containing the eumelanin‐inspired indole core have been successfully synthesized using common cross coupling reactions. These polymers differed by the arylene and the carbon–carbon bond linkage. Optoelectronic experiments of these polymers suggest that the ethynylene linkage contributed to the red‐shifted absorption spectra and blue‐shifted emission spectra when compared to the vinylene linkage polymers. Furthermore, the optical bandgaps of the poly(indoylenearyleneethynylene)s (PIAEs) were smaller compared to the poly(indoylenearylenevinylene)s (PIAVs). Surprisingly, the HOMOs of these polymers were less affected by the nature of the carbon–carbon linkage. However, the LUMOs of the PIAEs were lower in comparison to the PIAVs. These eumelanin‐inspired PIAEs and PIAVs are good fluorophores with fluorescence quantum yields ranging from 0.12 to 0.67 and have good thermal stability for applications such as in organic light‐emitting diodes. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 457–463     

Reductive Cleavage of Acetals/Ketals with ZrCl4/NaBH4

Reductive cleavage of acetals/ketals with zirconium tetrachloride-sodium borohydride leading to the formation of ether alcohols is described.