Solvent extraction of Np(IV) and Pu(IV) with mixtures of TOPO and HTTA

Solutions of HTTA are known to extract tetravalent actinides as M(TTA)₄ species. When TOPO is added to HTTA solutions, the extracting of Np(IV) and Pu(IV) from aqueous perchloric acid was enhanced enormously. The species responsible for the enhanced extraction were identified from the extraction data by the slope ratio method and JOB's method. It was found that the predominant species responsible for enhancement in the extraction, when [HTTA]≫[TOPO], was M(TTA)₄. TOPO for both Np(IV) and Pu(IV). Furthermore, it was established that depending on the relative concentrations of HTTA and TOPO, a number of species with the composition M(TTA)_a(ClO₄)_4-a·b TOPO, with a ranging from 1 to 4 and b having values of 1 or 2, are involved in the extraction. Several equilibrium constant values are given. Fuel Reprocessing Division.     

Ortho effects in organic molecules on electron impact 13—mechanism of decarboxylation in o-carboxy heteroaromatics

Expulsion of CO₂ from the molecular ions of the 2-(2-carboxyphenyl) derivatives of benzoxazole, benzothiazole and benzimidazole gives rise to the base peaks on electron impact. The proposed mechanism for this fragmentation process, involving the anchimeric assistance of the heteroatom by the initial abstraction of the H˙ from the carboxyl group followed by the expulsion of CO₂ from the molecular ions, is supported by the study of the linked scan spectra.     

Spectrographic analysis of high purity manganese dioxide

The fluoride content of aqueous and organic Purex process solutions can be determined with good reproducibility and accuracy. The method includes a distillation separation of fluoride and its subsequent electrometric determination using a fluoride-selective electrode. The analytical range covers 5 to 500 μg of fluoride per aliquot and the concentration limit is 5×10^?5 M (1 ppm). Complexing cations like Al(III), Zr(IV), La(III), and U(VI) do not interfere.     

Tuning energy landscapes and metal–metal interactions in supramolecular polymers regulated by coordination geometry

Herein, we exploit coordination geometry as a new tool to regulate the non-covalent interactions, photophysical properties and energy landscape of supramolecular polymers. To this end, we have designed two self-assembled Pt(ii) complexes 1 and 2 that feature an identical aromatic surface, but differ in the coordination and molecular geometry (linear vs. V-shaped) as a result of judicious ligand choice (monodentate pyridine vs. bidentate bipyridine). Even though both complexes form cooperative supramolecular polymers in methylcyclohexane, their supramolecular and photophysical behaviour differ significantly: while the high preorganization of the bipyridine-based complex 1 enables an H-type 1D stacking with short Pt⋯Pt contacts via a two-step consecutive process, the existence of increased steric effects for the pyridyl-based derivative 2 hinders the formation of metal–metal contacts and induces a single aggregation process into large bundles of fibers. Ultimately, this fine control of Pt⋯Pt distances leads to tuneable luminescence—red for 1vs. blue for 2, which highlights the relevance of coordination geometry for the development of functional supramolecular materials.

In this article, we exploit coordination geometry as a new tool to control the energy landscape and photophysical properties (red vs. blue luminescence) of supramolecular polymers.     

Synthetic Studies Toward Gangliosides and Their Analogs: Synthesis of Appropriately Protected Core Oligosaccharides as Construction Blocks

Abstract

2-(Trimethylsilyl)ethyl 2, 3, 6, 2′-tetra-O-acetyl-3′-O-benzyl-6′-O-benzyloxymethyl-β-d-lactoside (9) was synthesized starting from acetobromolactose (1) via 2-(trimethylsilyl)ethyl β-d-lactoside (3). Compound 9 was converted to the trisaccharide derivative 17 after coupling with 3,4,6-tri-O-acetyl-2-deoxy-2-phthalimido-α-d-galacto-pyranosyl bromide (11). Coupling of 17 with acetobromogalactose (19) gave the tetrasaccharide 20.     

Spectroscopy of laser-produced plasmas: Setting up of high-performance laser-induced breakdown spectroscopy system

It is a well-known fact that laser-induced breakdown spectroscopy (LIBS) has emerged as one of the best analytical techniques for multi-elemental compositional analysis of samples. We report assembling and optimization of LIBS set up using high resolution and broad-range echelle spectrograph coupled to an intensified charge coupled device (ICCD) to detect and quantify trace elements in environmental and clinical samples. Effects of variations of experimental parameters on spectroscopy signals of copper and brass are reported. Preliminary results of some plasma diagnostic calculations using recorded time-resolved optical emission signals are also reported for brass samples.     

Exotic decay in cerium isotopes

Half life for the emission of exotic clusters like ⁸Be, ¹²C, ¹⁶O, ²⁰Ne, ²⁴Mg and ²⁸Si are computed taking Coulomb and proximity potentials as interacting barrier and many of these are found well within the present upper limit of measurement. These results lie very close to those values reported by Shanmugam et al using their cubic plus Yukawa plus exponential model (CYEM). It is found that ¹²C and ¹⁶O emissions from ¹¹⁶Ce and ¹⁶O from ¹¹⁸Ce are most favorable for measurement (T _1/2<10¹⁰ s). Lowest half life time for ¹⁶O emission from ¹¹⁶Ce stress the role of doubly magic ¹⁰⁰Sn daughter in exotic decay. Geiger-Nuttall plots were studied for different clusters and are found to be linear. Inclusion of proximity potential will not produce much deviation to linear nature of Geiger-Nuttall plots. It is observed that neutron excess in the parent nuclei slow down the exotic decay process. These findings support the earlier observations of Gupta and collaborators using their preformed cluster model (PCM).     

Use of Ferric Chloride in Carbohydrate Reactions.1 Iv. Acetolysis of Benzyl Ethers of Sugars

Acetolysis of benzyl ethers of sugars has been carried out with anhydrous ferric chloride in acetic anhydride. By employing this reagent, benzyl ether groups variously placed in sugars or in their glycosides could be removed with ease and replaced by acetyl groups. By controlled acetolysis, preferential removal of certain benzyl groups was possible. The results show that in D-glucose the relative ease of removal of benzyl ether groups by acetolysis follows the order C-6 > C-4 > C-3 > C-2 and that the rate of acetolysis is 6-O-Bn : 3-O-Bn : 2-O-Bn = 125 : 24 : 1. The corresponding methyl ethers were very sluggish towards acetolysis.