Barrel- and crown-shaped dodecanuclear copper(II) cages built from phosphonate, pyrazole, and hydroxide ligands

The reaction of Cu(ClO4)2. 6H2O with t-BuP(O)(OH)2 and 3,5-(CF3)2PzH in the presence of triethylamine afforded the dodecanuclear cage ([Et3NH]2[Cu12(mu-3,5-(CF3)2Pz)6(mu3-OH)6(mu-OH)3(mu3-t-BuPO3)2(mu6-t-BuPO3)3][t-BuPO2OH][C6H5CH3]2) (2). The molecular structure of this cage revealed that it possesses a barrel-shaped architechture. The cage structure is built by the cumulative coordination action of phosphonate, hydroxide, and pyrazolyl ligands. A similar reaction involving Cu(NO3)2. 3H2O, t-BuP(O)(OH)2, 3,5-dimethylpyrazole, and triethylamine afforded another dodecanuclear cage [Cu12(mu-DMPz)8(eta1-DMPzH)2(mu4-O)2(mu3-OH)4(mu3- t-BuPO3)4].3MeOH (3). The latter is crown-shaped and is built by the coordination of pyrazole, pyrazolyl, phosphonate, hydroxide, oxide, and methanol ligands. Both of the dodecanuclear cages are efficient nucleases in the presence of magnesium monoperoxyphthalate.     

Synthesis and characterizations of BNT–BT–KNN ceramics for energy storage applications

Dielectric, ferroelectric and piezoelectric properties of the (0.94–x) Bi_0.5Na_0.5TiO₃–0.06BaTiO₃–xK_0.5Na_0.5NbO₃/BNT–BT–KNN ceramics with x = 0.02 and 0.05 (2KNN and 5KNN) were studied in detail. Dielectric study and temperature-dependent polarization hysteresis loops indicated a ferroelectric-to-antiferroelectric transition at depolarization temperature (T_d). The low T_d in both the ceramic samples suggested the dominant antiferroelectric ordering at room temperature (RT), which was also confirmed by RT polarization and strain hysteresis loops studies. Antiferroelectric-to-paraelectric phase transition temperature (T_m) was nearly same for both systems. The 5KNN ceramic samples showed the relaxor behaviour. The values of the dielectric constant, T_d, and maximum strain percentage increased, whereas the coercive field and remnant polarization decreased with the increase of the KNN percentage in the BNT–BT–KNN system. High-energy storage density ～0.5 J/cm³ at RT hinted about the suitability of the 5KNN system for energy storage applications.     

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.