Formation of left-handed helices in hybrid peptide oligomers with cis beta-sugar amino acid and L-Ala as building blocks

Residue based control of specific helical folding is explored in hybrid peptide oligomers consisting of alternating L-Ala and cis-beta-furanoid sugar amino acid (FSAA) residues as building blocks; two series of these hybrid oligomers are designed, synthesized and extensively characterized by using NMR, CD, FT-IR and MD simulation studies; results show the co-existence of left-handed 11- and 14/15-helical conformations in these short oligomers of Boc-(alpha/beta) and Boc-(beta/alpha) series.     

Confinement of the field electron emission to atomic sites on ultra sharp tips

The spatially controlled field assisted etching method for sharpening metallic tips, in a field ion microscope (FIM), is used to study the evolution of the field emission when the tip apex radius is decreased below 1 nm. Unlike the conventional image formation in a field emission microscope (FEM), we demonstrate that at this scale the field emission is rather confined to atomic sites. A single atom apex fabricated at the end of such tips exhibits an outstanding brightness compared to other atomic tips. The measurements have been repeated for two double atom tips, with different atom-atom separations, and images of atomic field emission localization have also been obtained. We have found that the field emission intensity alternates between adjacent atoms when the applied voltage is gradually increased beyond a threshold value.     

Enantioselective synthesis of (−)-lasubine II

A highly enantioselective synthesis of lythraceae alkaloid lasubine II has been achieved using organo-catalyzed Mannich reaction, Maruoka allylation, and aza-Michael addition as the key steps.     

Gold-catalyzed intramolecular hydroalkoxylation/cyclization of conjugated dienyl alcohols

Catalytic intramolecular additions of hydroxyl groups to tethered conjugated dienes are described. The reactions proceed smoothly at 60 °C in the presence of 5 mol % of (PPh₃)AuCl/AgOTf as a catalyst. A broad range of structurally diverse conjugated dienes produce substituted tetrahydrofurans and tetrahydropyrans in good yields. This reaction represents an atom-economic route to construct five- and six-membered cyclic ethers.     

Synthesis of α,α-dideutero-β-amino esters

A straight forward entry to α,α-dideutero-β-amino esters starting from the corresponding imines and deuterated acetonitrile has been developed involving a two-step process.     

Thermoluminescence response in gamma and UV irradiated Dy2O3 nanophosphor

Low temperature solution combustion method was employed to synthesize Dy₂O₃ nanophosphors using two different fuels (sugar and oxalyl dihydrazine (ODH)). Powder X-ray diffraction confirm pure cubic phase and the estimated particle size from Scherrer's method in sugar and ODH fuel was found to be 26 and 78 nm, respectively, and are in close agreement with those obtained using TEM and W–H plot analysis. SEM micrographs reveal porous, irregular shaped particles with large agglomeration in both the fuels. An optical band gap of 5.24 eV and 5.46 eV was observed for Dy₂O₃ for sugar and ODH fuels, respectively. The blueshift observed in sugar fuel is attributed to the particles size effect. Thermoluminescence (TL) response of cubic Dy₂O₃ nanophosphors prepared by both fuels was examined using gamma and UV radiations. The thermoluminescence of sugar used samples shows a single glow peak at 377 °C for 1–4 kGy gamma irradiations. When dose is increased to 5 kGy, two more shouldered peaks were observed at 245 and 310 °C. However, in TL of ODH used samples, a single glow peak at 376 °C was observed. It is observed that TL intensity is found to be more in sugar used samples. In UV irradiated samples a single glow peak at 365 °C was recorded in both the fuels with a little variation in TL intensity. The trapping parameters were estimated by different methods and the results are discussed.     

Selenadiazolopyridine: a synthon for supramolecular assembly and complexes with metallophilic interactions

The synthesis and characterization of the complexes of Cu(I), Ag(I), Cu(II), and Co(II) ions with 1,2,5-selenadiazolopyridine (psd) is reported. The following complexes have been prepared: [Cu(2)(psd)(3)(CH(3)CN)(2)](2+)2(PF(6)(-)); [(CuCl)(2)(psd)(3)]; [Cu(2)(psd)(6)](2+)2(ClO(4))(-); [Ag(2)(psd)(2)](2+)2(NO(3))(-); [Ag(2)(psd)(2)](2+)2(CF(3)COO)(-); [Cu(psd)(2)(H(2)O)(3)](2+)2(ClO(4))(-)·(psd)(2); [Cu(psd)(4)(H(2)O)](2+)2(ClO(4))(-)·(CHCl(3)); [Cu(psd)(2)(H(2)O)(3)](2+)2(NO(3))(-)·(H(2)O)·(psd)(2), and [Co(psd)(2)(H(2)O)(4)](2+)2(ClO(4))(-)·(psd)(2). The electronic structure of ligand psd, in particular the bond order of Se-N bonds, has been probed by X-ray diffraction, (77)Se NMR, and computational studies. A detailed analysis of the crystal structures of the ligand and the complexes revealed interesting supramolecular assembly. The assembly was further facilitated by the presence of neutral ligands for some complexes (Cu(II) and Co(II)). The molecular structure of the ligand showed that it was present as a dimer in the solid state where the monomers were linked by strong secondary bonding Se···N interactions. The crystal structures of Cu(I) and Ag(I) complexes revealed the dinuclear nature with characteristic metallophilic interactions [M···M] (M = Cu, Ag), while the Cu(II) and Co(II) complexes were mononuclear. The presence of M···M interactions has been further probed by Atoms in Molecules (AIM) calculations. The paramagnetic Cu(II) and Co(II) complexes have been characterized by UV-vis, ESI spectroscopy, and room temperature magnetic measurements.