Enantioselective total synthesis of (-)-zampanolide, a potent microtubule-stabilizing agent

An enantioselective total synthesis of zampanolide has been accomplished using a novel DDQ/Br?nsted acid promoted cyclization as the key reaction. The synthesis features cross-metathesis to construct the trisubstituted olefin and a ring-closing metathesis to form the macrolactone. The final N-acyl aminal formation was stereoselectively accomplished by an organocatalytic reaction.     

Selective colorimetric sensing of mercury(II) using turn off-turn on mechanism from riboflavin stabilized silver nanoparticles in aqueous medium

A simple Hg(2+) sensor has been developed using the vitamin B2 (riboflavin) stabilized Ag nanoparticle via a "turn off"-"turn on" mechanism; both the colour and photoluminescence properties of the riboflavin solution are used as sensitizing tools showing a sensitivity up to 5 nM Hg(2+) concentration.     

Concomitant synthesis of polyaniline and highly branched gold nanoparticles in the presence of DNA

The reduction of chloroauric acid using aniline adsorbed on DNA produces highly branched dendritic gold nanoparticles with concomitant formation of polyaniline (PANI) in contrast to the formation of spherical Au nanoparticles in the absence of DNA. The conformation of DNA remains intact in the process as evident from circular dichroism (CD) spectra. The UV-Vis spectrum exhibits a broad absorption peak at 520-900 nm, for a combined effect of the gold surface plasmon and π band to localized polaron band transition of DNA-doped PANI. Both the dendritic Au-PANI-DNA and the spherical Au-PANI systems emit two peaks for excitation with radiation of 300 nm and the intensity ratio of the emission and FRET peak is higher in the dendritic Au-PANI than that in the spherical Au-PANI system. The dc-conductivity values of spherical Au-PANI and dendritic Au-PANI-DNA systems are 1.2×10(-10) and 1.7×10(-8) S/cm at 30°C, respectively.     

Chiral pyridin-3-ones and pyridines: syntheses of enantiopure 2,4-disubstituted 6-hydroxy-1,6-dihydro-2H-pyridin-3-ones, 2,3-disubstituted 4-iodopyridines, and enantiopure 2,3-disubstituted 4-pyridinemethanols

The development of an innovative method to access enantiopure 2,4-disubstituted 6-hydroxy-1,6-dihydro-2H-pyridin-3-ones starting from D-glucal via the aza-Achmatowicz transformation has been described. These highly functionalized pyridin-3-ones have been utilized for the synthesis of contiguously substituted pyridines through a rapid and efficient Et(3)N/Ac(2)O promoted cyclo-elimination, aromatization cascade, allowing the facile assembly of important pyridine-based building blocks like 2-substituted 3-acetoxy-4-iodopyridines and enantiopure 2-substituted 3-acetoxy-4-pyridinemethanols possessing benzylic stereogenic centers, whose synthesis otherwise would be tedious. The utilization of commercially available sugars as starting materials, mild reaction conditions, catalytic transfer hydrogen (CTH) of α-furfuryl azide derivatives, transfer of chiral aryl/alkyl methanols from enulosides to pyridin-3-ones and pyridines, high yields, and short reaction times are key features of this method. The utility of the method has been further exemplified by demonstrating the usage of the 2-substituted 3-acetoxy-4-iodopyridine for the construction of biologically significant molecules like 2,7-disubstituted furo[2,3-c]pyridines and 7,7'-disubstituted 2,2'-bifuro[2,3-c]pyridines.     

A combinatorial formula for Macdonald polynomials

In this paper we use the combinatorics of alcove walks to give uniform combinatorial formulas for Macdonald polynomials for all Lie types. These formulas resemble the formulas of Haglund, Haiman and Loehr for Macdonald polynomials of type GLn. At q=0 these formulas specialize to the formula of Schwer for the Macdonald spherical function in terms of positively folded alcove walks and at q=t=0 these formulas specialize to the formula for the Weyl character in terms of the Littelmann path model (in the positively folded gallery form of Gaussent and Littelmann).     

Synthesis and characterization of K2NiF4-type phases Ln0.5Sr1.5Mn0.5Fe0.5O4 (Ln = La, Nd, Gd, and Dy)

A systematic investigation of layered perovskite oxides with general formula Ln_0.5Sr_1.5Mn_0.5Fe_0.5O₄ (Ln?=?La, Nd, Gd, and Dy) has been undertaken mainly to understand their structural, magnetic, as well as electrical behavior. The materials were prepared by the ceramic method. X-ray data have been analyzed by using program Checkcell and the variations of various parameters are explained. It has been concluded that not only A-site cation radius, <r _A>, but also the size variance factor (σ ²) influence electrical and magnetic properties. A systematic study of electrical resistivity of all the four materials was undertaken as a function of temperature to understand the conduction mechanism. On analyzing the electrical resistivity data, it has been concluded that variable range hopping model is found to fit well. The magnetic studies suggest that the phases are antiferromagnetic and this behavior could arise from Mn⁴⁺–O–Mn⁴⁺, and Fe³⁺–O–Fe³⁺ superexchange interaction.     

Chiral discrimination in biomimetic systems: Phenylalanine

Chiral discrimination and recognition is important in peptide biosynthesis, amino acid synthesis and drug designing. Detailed structural information is available about the peptide synthesis in ribosome. However, no detailed study is available about the discrimination in peptide synthesis. We study the conformational energy variation of neutral methoxy phenyl alanine molecule as a function of its different dihedral angle to locate the minimum energy conformation using quantum chemical theory. We compared the intermolecular energy surfaces of phenyl alanine molecule in its neutral and zwitterionic state using quantum chemical theory as a function of distance and mutual orientation. The energy surfaces are studied with rigid geometry by varying the distance and orientation. The potential energy surfaces of L-L and D-L pairs are found to be dissimilar and reflect the underlying chirality of the homochiral pair and racemic nature of the heterochiral pair. The intermolecular energy surface of homochiral pair is more favourable than the corresponding energy surface of heterochiral pair.     

Fiber-optic acoustic sensor for nondestructive evaluation

An experimental study was conducted to investigate the applicability of fiber-optic acoustic sensors to detect internal flaws in polymeric materials. A polarimetric fiber-optic sensor embedded in a plexiglass model received the acoustic signals generated by an ultrasonic transducer. It is shown that proper control of the polarization and phase of the optical beam is required to obtain meaningful results from the amplitude of the fiber-optic sensor signal. The sensor has shown promising results in determining acoustical properties of plexiglass and locating internal defects. The attractive feature of this sensing scheme is that the optical fibers are not modified prior to embedding. Therefore, they preserve their mechanical properties which makes the embedding process much easier.