Oxidative amidation of benzyl alcohols with amino acid esters mediated by N-hydroxysuccinimide/phenyliodine diacetate

A simple protocol involving metal-free oxidative amidation of benzyl alcohols with amino acid esters has been presented. The amidation proceeds in a radical pathway unlike in conventional metal-mediated extrusion of dihydrogen. The method is advantageous in terms of metal-free conditions, nonexpensive commercial starting substrates. Also various substituents in the starting materials are tolerated and sterically hindered amino acid side chains could provide good yields of amide products.     

Singular Propositions,Negation and the Square of Opposition

This paper contains two traditions of diagrammatic studies namely one, the Euler–Venn–Peirce diagram and the other, following tradition of Aristotle, the square of oppositions. We put together both the traditions to study representations of singular propositions (through a diagram system Venn-i, involving constants), their negations and the inter relationship between the two. Along with classical negation we have incorporated negation of another kind viz. absence (taking a cue from the notion of ‘abhãva’ existing in ancient Indian knowledge system). We have also considered the changes that take place in the context of open universe.     

One‐pot direct synthesis of fluorescent polyaniline‐porphyrin macrospheres from porphyrin

Porphyrins are very important chromophores as sensitizer in solar cell. Hole and electron transport layers are being used as an important layer to move the electrons and holes away from the sensitizer molecule to electrodes. In this work, a simple process has been developed for the synthesis of one layer combination of sensitizer and hole transport, that is, polyaniline‐porphyrin (PANI‐TPPS₄) system as a bulk heterojunction. Macrospheres of fluorescent PANI‐TPPS₄ materials were synthesized by one‐pot as well as two step processes directly from porphyrin for the first time. The advantage of this process is no need to isolate sulfonated porphyrin (TPPS₄), which is a difficult process. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Tetramethylguanidinium‐polyallylamine (Tmg‐PA): A new class of nonviral vector for efficient gene transfection

Highly toxic polyallylamine (PA) was reacted with a varying amount of a novel linker, 6‐(N,N,N′,N′‐tetramethylguanidinium chloride) hexanoic acid (Tmg‐HA), to prepare a series of tetramethylguanidinium‐PA (Tmg‐PA) polymers, which were used as vectors for gene transfection. The extent of attachment of the linker, Tmg‐HA, to the PA backbone was determined by 2,4,6‐trinitrobenzene sulfonic acid assay. The modified polymers (Tmg‐PAs), when complexed with pDNA, exhibited good condensation ability. The nanoparticles, so formed, were characterized by their size and zeta potential and were subsequently evaluated for their toxicity and transfection ability on various mammalian cells, viz., HeLa, CHO, and HEK 293 cells. Mobility shift assay revealed that on increasing the percent substitution of Tmg‐HA onto PA (from Tmg‐PA1 to Tmg‐PA6), relatively higher amounts of modified polymers were required to retard the mobility of a fixed amount of DNA. Besides, Tmg‐PA polymers provided sufficient protection (ca. 84–88%) to bound DNA against nucleases and one of the formulations, Tmg‐PA2 (ca. 15% substitution) displayed the highest transfection efficiency outcompeting the commercial transfection reagent, Lipofectamine? with minimal cytotoxicity. More impressively, the transfection efficiency increased despite recording a decrease in the buffering capacity of the grafted polymers suggesting that buffering capacity is not the sole parameter in determining the gene delivery efficiency of a vector system. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Imidazole derivatives as the organic precursor of ZnO nano particle

N₁-Hydroxy-2,4,5-trisubstituted imidazoles were synthesized starting from 1,2-diketones. The crystal structure of 4,5-dimethyl-2-(3-nitrophenyl)-1H-imidazol-1-ol has been determined. An unusual intermolecular hydrogen bonding through the association of water molecule has been reported. These imidazole derivatives can be thought of as the organic precursor for the synthesis of zinc oxide nano particles.     

Characterization and photoluminescence properties of some MLn2(1−x)O4:2xEu or 2xTb systems (M=Ba or Sr, Ln=Gd or La)

BaGd₂O₄, BaLa₂O₄ and SrLa₂O₄ powders doped with different concentrations of Eu³⁺ or Tb³⁺ are prepared by combustion synthesis method and the samples were further heated to 500, 700 and 900 °C to improve the crystallinity of the materials. The structure and morphology of materials have been examined by X-ray diffraction and scanning electron microscopy. It is remarkable that all the samples of BaGd₂O₄, BaLa₂O₄ and SrLa₂O₄ have similar morphology. The SEM images show homogeneous aggregates of varying shapes and sizes, which are composed of a large number of small elliptical shaped crystallites with an average diameter of about 0.5-3.0 μm. Photoluminescence for all materials increases with increase of temperature and shows a maximum for the samples heated to 900 °C with 4 mole% doping of Eu³⁺ or Tb³⁺ ions. The luminescence is almost same for all powders when doped with same concentration of Eu³⁺.     

Catalyst electronic polarizability and enantiomeric excess in asymmetric hydrogenation

In the classical rhodium-diphosphine complexes-catalyzed asymmetric hydrogenation of enamide substrates, examination on the role of catalyst electronic polarizability in the origin of enantioselectivity reveals its linear free energy relationship with the product enantiomeric ratio that is much more pronounced than analogous correlation with steric effect in the same systems. From a conceptually novel scenario, this work suggests that the often-overlooked chiral catalyst local polarizability property may function as a controlling force in enantioselection thus has important implication in rational catalyst design.