The local environment of Co2+ ions intercalated in vanadium oxide/hexadecylamine nanotubes

Vanadium oxide nanotubes constitute promising materials for applications in nanoelectronics as cathode materials, in sensor technology and in catalysis. In this work we present a study on hybrid vanadium oxide/hexadecylamine multiwall nanotubes doped with Co ions using state of the art x-ray diffraction and absorption techniques, to address the issue of the dopant location within the nanotubes' structure. The x-ray absorption near-edge structure analysis shows that the Co ions in the nanotubes are in the 2+ oxidation state, while extended x-ray absorption fine structure spectroscopy reveals the local environment of the Co2+ ions. Results indicate that Co atoms are exchanged at the interface between the vanadium oxide's layers and the hexadecylamines, reducing the amount of amine chains and therefore the interlayer distance, but preserving the tubular shape. The findings in this work are important for describing Co2+ interaction with vanadium oxide nanotubes at the molecular level and will help to improve the understanding of their physicochemical behavior, which is desired in view of their promising applications.

Enhancement of Electrical Conductivity in Plasticized Chitosan Based Membranes

Plasticized natural macromolecules-based polymer electrolyte samples were prepared and characterized. The plasticization of chitosonium acetate with glycerol increased the ionic conductivity value from 3.0 x 10(-7) S/cm to 1.1 x 10(-5) S/cm. The conductivity temperature relationship of the samples exhibits either VTF or Arrhenius type depending on the glycerol concentration in the sample. The dielectric studies evidencing the relaxation process in the plasticized sample at low frequency region are due to the electric polarization effect. Moreover, the samples were transparent in the Vis region, showed thermal stability up to 160 degrees C and good surface uniformity.

Gellan Gum-LiI Gel Polymer Electrolytes

Gellan-based polymer electrolytes (PEs), doped with lithium iodide (LiI), were prepared and their electrical properties were characterized. The samples are thermally stable up to 234 degrees C and exhibit ionic conductivity of 3.8 x 10(-4) S/cm at room temperature for the sample doped with 40 wt% of LiI. Addition of 10 wt% of glycerol promotes an increase of the ionic conductivity to 1.5 x 10(-3) S/cm, which remains stable up to 100 degrees C. The activation energies of 2.4 to 12.4 kJ/mol were derived from the Arrhenius model. The repeated ionic conductivity measurements as a function of temperature show that these membranes can be reversibly used between the room temperature and 100 degrees C.

A Facile, Versatile, and Mild Morita-Baylis-Hillman-Type Reaction for the Modular One-Pot Synthesis of Highly Functionalized MBH Adducts

MoritaBaylisHillman derivatives have been extensively investigated as intermediates in the preparation of important classes of compounds. However, there are intrinsic limitations regarding the structure of the Michael electrophile acceptors, the aldehydes, and the catalysts. Therefore, this transformation has several drawbacks, including, for example, its long reaction times. Herein we present a simple, general, fast, and high-yielding protocol for the one-pot synthesis of MoritaBaylisHillman derivatives. Our approach is driven by a lithium selenolate Michael/aldol operation with concomitant O-functionalization/selenoxide elimination cascade sequences.

Efeito do lítio sobre a hiperatividade locomotora induzida pela lesão eletrolítica da região do núcleo mediano da rafe em ratos

A lesão do núcleo mediano da rafe (NMR) produz sintomas que sugerem validade de face ao episódio maníaco. Esta pesquisa avaliou o efeito do lítio sobre a hiperatividade locomotora induzida por esta lesão. Vinte e um ratos Wistar machos foram submetidos à lesão eletrolítica da região do NMR (LR) e 17 foram submetidos à lesão fictícia (LF). Após recuperação, a atividade locomotora foi avaliada na caixa de atividade (Med Associates/ENV-515). Parte dos animais destes grupos recebeu tratamentos com lítio (47,5 mg/kg/2x dia i.p.) por 10 dias, enquanto o restante foi tratado com salina no mesmo esquema. A reavaliação ao final dos tratamentos demonstrou que o lítio reduziu significantemente a atividade locomotora em relação à avaliação inicial no grupo LR (ANOVA/Bonferroni p < 0,05), tornando-a equivalente aos baixos níveis dos grupos LF. Estes dados sustentam a hipótese de que as manifestações induzidas pela lesão do NMR podem constituir um modelo animal de mania.

Autoionizing states and their relevance in electron-ion recombination

Atomic physics plays an important role in determining the evolution stages in a wide range of laboratory and cosmic plasmas. Therefore, the main contribution to our ability to model, infer and control plasma sources is the knowledge of underlying atomic processes. Of particular importance are reliable low temperature dielectronic recombination (DR) rate coefficients. This thesis provides systematically calculated DR rate coefficients of lithium-like beryllium and sodium ions via ∆n = 0 doubly excited resonant states. The calculations are based on complex-scaled relativistic many-body perturbation theory in an all-order formulation within the single- and double-excitation coupled-cluster scheme, including radiative corrections. Comparison of DR resonance parameters (energy levels, autoionization widths, radiative transition probabilities and strengths) between our theoretical predictions and the heavy-ion storage rings experiments (CRYRING-Stockholm and TSRHeidelberg) shows good agreement. The intruder state problem is a principal obstacle for general application of the coupled-cluster formalism on doubly excited states. Thus, we have developed a technique designed to avoid the intruder state problem. It is based on a convenient partitioning of the Hilbert space and reformulation of the conventional set of pairequations. The general aspects of this development are discussed, and the effectiveness of its numerical implementation (within the non-relativistic framework) is selectively illustrated on autoionizing doubly excited states of helium.

Asymmetric synthesis of benzylic and heterobenzylic amines

C2-Symmetrical, enantiopure 2,6-di[1-(1-aziridinyl)alkyl]pyridines (DIAZAPs) were prepared by a high-yielding, three-step sequence starting from 2,6-pyridinedicarbaldehyde and (S)-valinol or (S)-phenylglycinol. The new compounds were tested as ligands in palladium-catalyzed allylation of carbanions in different solvents. Almost quantitative yield and up to 99% enantiomeric excess were obtained in the reactions of the enolates derived from malonate, phenyl- and benzylmalonate dimethyl esters with 1,3-diphenyl-2-propenyl ethyl carbonate. Asymmetric synthesis of 2-(2-pyridyl)aziridines from chiral 2-pyridineimines bearing a stereogenic center at the nitrogen atom was development. The envisioned route involves the addition of chloromethyllithium to the imine derived from 2-pyridinealdehyde and (S)-valinol, protected as O-trimethylsilyl ether. The analogous reaction performed on the imine derived from (S)-valine methyl ester gave the product containing the aziridine ring as well as the α-chloro ketone group coming from the attack of chloromethyllithium to the ester function. Other stereogenic alkyl substituents at nitrogen gave less satisfactory results. Moreover, the aziridination protocol did not work on other aromatic imines, e.g. 3-pyridineimine and benzaldimine, which are not capable of bidentate chelation. The N-substituent could not be removed, but aziridine underwent ring-opening by attack of nitrogen, sulfur, and oxygen nucleophiles. Complete or prevalent regioselectivity was obtained using cerium trichloride heptahydrate as a catalyst. In some cases, the N-substituent could be removed by an oxidative protocol. The addition of organometallic (lithium, magnesium, zinc) reagents to 2-pyrroleimines derived from (S)-valinol and (S)-phenylglycinol gave the N-substituted-1-(2-pyrrolyl)alkylamines with high yields and diastereoselectivities. The (S,S)-diastereomers were useful intermediates for the preparation of enantiopure 1-[1-(2-pyrrolyl)alkyl]aziridines by routine cyclization of the β-aminoalcohol moiety and of (S)-N-benzoyl 1-[1-(2-pyrrolyl)alkyl]amines and their N-substituted derivatives by oxidative cleavage of the chiral auxiliary. 1-Allyl-2-pyrroleimines obtained from (S)-phenylglycinol and (S)-valinol underwent highly diastereoselective addition of allylmetal reagents, used in excess amounts, to give the corresponding secondary amines with concomitant allyl to 1-propenyl isomerisation of the 1-pyrrole substituent. Protection of the 2-aminoalcohol moiety as oxazolidinone, amide or Boc derivate followed by ring closing metathesis of the alkene groups gave the unsaturated bicyclic compound, whose hydrogenation afforded the indolizidine derivative as a mixture of separable diastereomers. The absolute configuration of the main diastereomer was assessed by X-ray crystallographic analysis.