Trace element determination in thorium oxide using total reflection X-ray fluorescence spectrometry

Applicability of Total Reflection X-ray Fluorescence (TXRF) spectrometry for the determination of trace metals at concentration of µg/g level in thorium oxide was studied. The TXRF spectrometer was calibrated using a multielement standard solution and the method was validated by analyzing another multielement standard solution. Sample preparation conditions were optimized for the TXRF determinations of trace metals in thorium oxide. The elements K, Ca, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sr, Y, Ba and Pb present in thorium oxide standards were determined after dissolving them in HNO₃/HF mixture and separating the bulk matrix, thorium, by solvent extraction using tri-n-butyl phosphate (TBP) and tri-n-octyl phosphine oxide (TOPO) as extractants. A comparison of TXRF determined concentrations of trace elements Ca, V, Cr, Mn, Fe, Ni and Cu with the certified values shows that TXRF determined concentrations have an RSD of 20% (1 s for n = 4) and are within an agreement of 20% of the certified values in most of the cases.     

Crowd dynamics through non-local conservation laws

We present a Lax-Friedrichs type scheme to compute the solutions of a class of non-local and non-linear systems of conservation laws in several space dimensions. The convergence of the approximate solutions is proved by providing suitable L¹, L^∞ and BV uniform bounds. To illustrate the performances of the scheme, we consider an application to crowd dynamics. Numerical integrations show the formation of lanes in groups moving in opposite directions. This is joint work with R.M. Colombo (INDAM Unit, University of Brescia).     

Giant Hysteretic Sorption of CO2: In Situ Crystallographic Visualization of Guest Binding within a Breathing Framework at 298 K

A dynamic Zn^II‐MOF has been shown to exhibit extreme breathing behavior under gas pressure. The very narrow pore form of the activated framework opens up in the presence of carbon dioxide, thus making it a suitable material for CO₂ capture. Sorption of CO₂ at 298 K and relatively high pressure clearly shows a two‐step isotherm with giant hysteresis for the second step. In‐situ single‐crystal diffraction analysis was carried out under CO₂ gas pressure at 298 K using an environmental gas cell in order to visualize the interaction between CO₂ and the host framework. The results are well supported by pressure‐gradient differential scanning calorimetry (P‐DSC) and variable‐pressure powder X‐ray analysis. Theoretical calculations have been carried out in order to further back up the crystallographic data.     

Pyrazolo[1,5-a]pyrimidines. A combined multinuclear magnetic resonance (1H, 13C, 15N, 19F) and DFT approach to their structural assignment

Multinuclear magnetic resonance spectroscopy together with GIAO-DFT calculations allowed establishment of the structure of the products obtained by condensation of 3(5)-amino-4-phenyl-1H-pyrazole and beta-dicarbonyl compounds bearing a trifluoromethyl group. They are 3-phenyl-5-(R)-7-trifluoromethylpyrazolo[1,5-a]pyrimidines.     

Effect of High Humidity Exposure to Wheat Starch Based High Conducting Flexible Polymer-in-Salt-Electrolyte

Polymer-in-salt-electrolytes (PISEs) are an important class of electrolytes as they carry the promise of faster and single ion transport. Unfortunately, due to unavailability of a suitable polymer host PISE has still not reached to commercial level. In the present work, using a novel synthesis protocol developed by the group, glutaraldehyde crosslinked wheat starch has been successfully modified with sodium iodide (NaI) to synthesize a flexible PISE membrane with desired electrochemical properties. Present paper reports the effect of crosslinker and exposure to high humidity ambience on electrochemical and morphological properties. It has been established that on exposure to higher humidity atmosphere starch-based PISEs stabilize at lower resistance value, but with higher ion relaxation time, which indicates that effect of high humidity treatment is more on salt dissociation instead of assisting the ion transport. The studied materials have conductivity ≈0.01 S cm⁻¹ range with ESW >2.5 V, ensuring its usability in electrochemical devices. The developed synthesis protocol does not require any complicated synthesis route and/or sophisticated instrument hence the overall process is economical also, adding up to its potentiality for energy device fabrication.     

Synthesis,characterization and spectroscopic studies of a new ligand [N′-(2-methoxybenzoyl)hydrazinecarbodithioate] ethyl ester and its Mn(II) and Cd(II) complexes: X-ray structural study of Mn(II) complex

A new dithioligand [N′-(2-methoxybenzoyl)hydrazinecarbodithioate] ethyl ester (H₂mbhce, 1) formed complexes [M(Hmbhce)₂]_n {M = Mn(II), Cd(II)} which have been characterized with the help of elemental analyses, magnetic susceptibility measurements, IR, UV–Vis, ¹H and ¹³C NMR and mass spectrometry. [Mn(Hmbhce)₂]_n (2) crystallized in monoclinic system with space group P₂₁/n. In the polymeric structure of 2, the ligand acts as an uninegative tridentate N(1), O(1), S(3) donor and forms a five membered chelate ring with N(1), C(2) and O(1). The intermediate bond lengths (between single and double bond distances) O(1)–C(2) = 1.241(3), N(2)–C(2) = 1.325(3), N(1)–N(2) = 1.393(2), N(1)–C(8) = 1.311(3) ? and C(8)–S(3) = 1.704(2) Å suggest considerable delocalization of charge which develops slightly aromatic character in the chelate ring.     

Enhanced Catalytic Activity and Unexpected Products from the Oxidation of Cyclohexene by Organic Nanoparticles of 5,10,15,20‐Tetrakis‐(2,3,4,5,6‐pentafluorophenyl)porphyrinatoiron(III) in Water by Using O2

The catalytic oxidation of alkenes by most iron porphyrins using a variety of oxygen sources, but generally not dioxygen, yields the epoxide with minor quantities of other products. The turnover numbers for these catalysts are modest, ranging from a few hundred to a few thousand depending on the porphyrin structure, axial ligands, and other reaction conditions. Halogenation of substituents increases the activity of the metalloporphyrin catalyst and/or makes it more robust to oxidative degradation. Oxidation of cyclohexene by 5,10,15,20‐tetrakis‐(2,3,4,5,6‐pentafluorophenyl)porphyrinato iron(III), ([Fe^III(tppf₂₀)]) and H₂O₂ is typical of the latter: the epoxide is 99 % of the product and turnover numbers are about 350. 1 – 4 Herein, we report that dynamic organic nanoparticles (ONPs) of [Fe^III(tppf₂₀)] with a diameter of 10 nm, formed by host–guest solvent methods, catalytically oxidize cyclohexene with O₂ to yield only 2‐cyclohexene‐1‐one and 2‐cyclohexene‐1‐ol with approximately 10‐fold greater turnover numbers compared to the non‐aggregated metalloporphyrin in acetonitrile/methanol. These ONPs facilitate a greener reaction because the reaction solvent is 89 % water and O₂ is the oxidant in place of synthetic oxygen sources. This reactivity is unexpected because the metalloporphyrins are in close proximity and oxidative degradation of the catalyst should be enhanced, thus causing a significant decrease in catalytic turnovers. The allylic products suggest a different oxidative mechanism compared to that of the solvated metalloporphyrins. These results illustrate the unique properties of some ONPs relative to the component molecules or those attached to supports.     

Asymmetric Hydroboration of 1,1‐Disubstituted Alkenes

A breakthrough in the asymmetric hydroboration of notoriously difficult 1,1‐disubstituted alkenes using a new family of highly effective hydroboration reagents is described (see scheme). The intermediate boranes can be oxidized to alcohols or used in Suzuki–Miyaura cross‐coupling reactions.

     

Monodisperse Co,Zn-Ferrite nanocrystals: Controlled synthesis,characterization and magnetic properties

Co_xZn_yFe_3−x−yO₄ ferrite (x=1 to 0; y=0 to1) nanocrystals have been synthesized by reverse microemulsion method. The nanocrystals are then comprehensively characterized by X-ray diffraction, Fourier transform infrared spectroscopy, Field emission transmission electron microscopy (FETEM), and magnetic properties were measured by using Vibrating sample magnetometer. X-ray analysis showed that all the crystals were cubic spinel. The lattice constant increased with the increase in Zn substitution. FETEM reveals that particle size varies in the range from 3 to 6 nm. As the concentration of Zn increases the magnetic behavior varies from ferromagnetic at y=0 and 0.2 to superparamagnetic to paramagnetic at y=1. The Curie temperature decreases with increasing concentration of Zn.     

The characterisation of the smallest two fold blocking sets in PG(<Emphasis Type="Italic">n</Emphasis>, 2)

We classify the smallest two fold blocking sets with respect to the (n−k)-spaces in PG(n, 2). We show that they either consist of two disjoint k-dimensional subspaces or are equal to a (k + 1)-dimensional space minus one point.