Reverse micellar synthesis and properties of nanocrystalline GMR materials (LaMnO3, La0.67Sr0.33MnO3 and La0.67Ca0.33MnO3): Ramifications of size considerations

Nanoparticles of complex manganites (viz. LaMnO₃, La_0.67Sr_0.33MnO₃ and La_0.67Ca{0.33}MnO₃) have been synthesized using the reverse micellar route. These manganites are prepared at 800‡C and the monophasic nature of all the oxides has been established by powder X-ray diffraction studies. TEM studies show an average grain size of 68, 80 and 50 nm for LaMnO₃, La_0.67Sr_0.33MnO₃ and La_0.67Ca{0.33}MnO₃respectively. Ferromagnetic ordering is observed at around 250 K for LaMnO₃, 350 K for La_0.67Sr_0.33MnO₃ and 200 K for La_0.67Ca{0.33}MnO₃. These Curie temperatures correspond well with those reported for bulk materials with similar composition.     

Synthesis of graft copolymers with “V‐shaped” and “Y‐shaped” side chains via controlled radical and anionic polymerizations

A combination of nitroxide‐mediated radical polymerization and living anionic polymerization was used to synthesize a series of well‐defined graft (co)polymers with “V‐shaped” and “Y‐shaped” branches. The polymer main chain is a copolymer of styrene and p‐chloromethylstyrene (PS‐co‐PCMS) prepared via nitroxide‐mediated radical polymerization. The V‐shaped branches were prepared through coupling reaction of polystyrene macromonomer, carrying 1,1‐diphenylethylene terminus, with polystyryllithium or polyisoprenyllithium. The Y‐shaped branches were prepared throughfurther polymerization initiated by the V‐shaped anions. The obtained branches, carrying a living anion at the middle (V‐shaped) or at the end of the third segment (Y‐shaped), were coupled in situ with pendent benzyl chloride of PS‐co‐PCMS to form the target graft (co)polymers. The purified graft (co)polymers were analyzed by size exclusion chromatography equipped with a multiangle light scattering detector and a viscometer. The result shows that the viscosities and radii of gyration of the branched polymers are remarkably smaller than those of linear polystyrene. In addition, V‐shaped product adopts a more compact conformation in dilute solution than the Y‐shaped analogy. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4013–4025, 2007     

Clustering study in Eu(DBM)3Phen-doped polymer optical fibers by optical properties and near-field scanning microscopy

The clusters of Eu3+ ion in Eu(DBM)3Phen-doped polymethyl methacrylate (PMMA) have been studied by three means. The relative fluorescence intensity ratio of the 5D0 → 7F2 to 5D0 → 7F1 transitions with different concentrations of Eu3+ in Eu(DBM)3Phen-doped PMMA and metastable-state (5D0) lifetime dependence on Eu3+ concentration are analyzed. The analysis indicates that there are no clustering effects in Eu3+ ions of Eu(DBM)3Phen-doped PMMA when the Eu3+ doping concentration is up to 1.0 wt.-%. At the same time, the clustering effect has not been observed by the scanning near-field optical microscopy (SNOM) in Eu(DBM)3Phen-doped PMMA with 1.0 wt.-% of Eu3+ ions. The analysis reveals that a high concentration of Eu3+ can be incorporated into polymer optical fiber (POF) without clustering effect.OCIS codes: 180.5810, 300.6280, 250.5460, 160.5690.     

Photocatalytic Synthesis of Oxygenates from Gaseous CO2 and CH4 over Semiconductor

Photoinduced synthesis of CO2 and CH4 was investigated using a batch reaction system on several photoactive materials supported on silicon dioxide. Single semiconductor showed higher selectivity to C1 compounds. The production of C2-C3 oxygenates took place preferentially on composite semiconductor photocatalysts. In particular, it was found that acetone was the primary product over Cu/CdS-TiO2/SiO2.     

An Efficient, One-Pot Synthesis of Carbamates from the Corresponding Alcohols Using Mitsunobu’s Reagent

A novel Mitsunobu-based protocol was developed for the synthesis of carbamates from the corresponding alcohols using carbon dioxide and amines in good to excellent yields. This protocol is mild, chemoselective, and efficient compared to other reported methods.     

Adsorption of dicarboxylates on nano-sized gibbsite particles: effects of ligand structure on bonding mechanisms

The adsorption of the dicarboxylates o-phthalate, maleate, fumarate, malonate, and oxalate (representing ligands with the general composition ⁻O₂C---C_n---CO₂⁻; n=0, 1, or 2) on gibbsite were studied by means of quantitative batch adsorption experiments and attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy. The interpretations of ATR-FTIR spectra were aided by comparison with IR spectra of solution species and by results from theoretical frequency calculations. The main objectives of the study were to identify the molecular level bonding mechanisms of the dicarboxylates to gibbsite, and to investigate how these were influenced by the composition and structure of the ligands. Carboxylates with n=2 formed predominantly outer sphere complexes, whereas the importance of inner sphere complexes progressively increased for n=1 and 0. The inner sphere structures were identified as mononuclear chelates with one oxygen from each carboxylate group bonded to Al(III) at the surface. This showed the importance of chelate ring structure for the formation of inner sphere surface complexes, with stabilities of the complexes increasing in the order seven-membered ring less than six-membered ring less than five-membered ring. For ligands with n=2 only small variations in surface speciation were observed as a function of steric factors; irrespective of the relative positions of the carboxylate groups and bulkiness of the ligands outer sphere bonding is the dominating adsorption mode. Adsorption experiments were also conducted with gibbsite particles exhibiting differences in shape and surface roughness. These experiments showed that inner sphere complexes were favored on the less well-developed and more irregular gibbsite particles.     

The supersymmetric WKB approximation of ring-shaped oscillator potential in r and θ dimensions with spherical polar coordinates

According to calculation of the energy spectrum of ring-shape oscillator potential by using the supersymmetric WKB approximation, it is shown that the energy spectrum of some noncentral separable potentials can be exactly obtained in r and θ dimensions by above method.     

Difference schemes on uniform grids performed by general discrete operators

Our aim is to set the foundations of a discrete vectorial calculus on uniform n-dimensional grids, that can be easily reformulated on general irregular grids. As a key tool we first introduce the notion of tangent space to any grid node. Then we define the concepts of vector field, field of matrices and inner products on the space of grid functions and on the space of vector fields, mimicking the continuous setting. This allows us to obtain the discrete analogous of the basic first order differential operators, gradient and divergence, whose composition define the fundamental second order difference operator. As an application, we show that all difference schemes, with constant coefficients, for first and second order differential operators with constant coefficients can be seen as difference operators of the form for suitable choices of q, and  . In addition, we characterize special properties of the difference scheme, such as consistency, symmetry and positivity in terms of q, and  .