Some observations on the synthesis and HPLC of tris-(acetylacetonato)technetium(III) and (IV) complexes

[⁹⁹Tc(III) (acac)₃] was synthesized by published procedure, but recovered by extraction into CH₂Cl₂. The product was purified by preparative HPLC over a reversed phase column, RP18, using a mobile phase of 11 CH₃OHH₂O. The cationic complex [⁹⁹Tc(IV) (acac)₃]⁺ prepared by the oxidation of the purified neutral Tc(III) complex was unstable in methanol/methanol-water medium, being reduced back to the Tc(III) complex.     

Inclusion of α-phenyl-N-p-methylphenyl Nitrone in β- Cyclodextrin: Formation of 1G : 1H and 1G : 2H Complexes and the Remarkably Fast 1,3-Dipolar Cycloaddition of the 1G : 2H Complex with Olefins in the Solid State

The nitrone is found to be included in the -cyclodextrin cavity in two different stoichiometries viz., 1G : 1H and 1G : 2H – the existence of which is proved by physical methods. The 1G : 2H complex of the nitrone serves as a good potent dipolarophile in the 1,3-dipolar cycloaddition reactions with olefins resulting in rate acceleration and regioselection.     

Ab initio study of (13)C(alpha) chemical shift anisotropy tensors in peptides

This study reports magnitudes and the orientation of the (13)C(alpha) chemical shift anisotropy (CSA) tensors of peptides obtained using quantum chemical calculations. The dependency of the CSA tensor parameters on the energy optimization of hydrogen atom positions and hydrogen bonding effects and the use of zwitterionic peptides in the calculations are examined. Our results indicate that the energy optimization of the hydrogen atom positions in crystal structures is necessary to obtain accurate CSA tensors. The inclusion of intermolecular effects such as hydrogen bonding in the calculations provided better agreement between the calculated and experimental values; however, the use of zwitterionic peptides in calculations, with or without the inclusion of hydrogen bonding, did not improve the results. In addition, our calculated values are in good agreement with tensor values obtained from solid-state NMR experiments on glycine-containing tripeptides. In the case of peptides containing an aromatic residue, calculations on an isolated peptide yielded more accurate isotropic shift values than the calculations on extended structures of the peptide. The calculations also suggested that the presence of an aromatic ring in the extended crystal peptide structure influences the magnitude of the delta(22) which the present level of ab initio calculations are unable to reproduce.     

Cellulose acetate and polyethersulfone blend ultrafiltration membranes. Part I: Preparation and characterizations

The overall objective of this investigation is to achieve high‐performance membranes with respect to flux and rejection characteristics, with an interplay of blending polymers having desired qualities. Thus, cellulose diacetate and polyethersulfone as candidate materials, in the presence of polyethylene glycol 600 as a pore forming agent, were blended in 100/0, 95/5, 90/10, 85/15, 80,20 and 75/25% compositions using N,N′‐dimethylformamide as solvent and membranes were prepared by the phase inversion technique. Polymer blend composition, additive concentration, and casting and gelation conditions were standardized for the preparation of asymmetric membranes with various pore statistics and morphology. These blend membranes were characterized for compaction in ultrafiltration experiments at 414 kPa pressure in order to attain steady state flux and is reached within 4–5 hr. The pure water flux was measured at 345 kPa pressure and is determined largely by the composition of polyethersulfone and additive concentration. The flux was found to reach the highest values of 66.5 and 275 1/(cm² hr) at 0 and 10 wt% additive concentrations respectively, at 25% SPS content of the blend. Membrane hydraulic resistance derived by measuring water flux at various transmembrane pressure and by using an algorithm was found to be inversely proportional to pure water flux. Water content is estimated by simple drying and weighing procedures and found proportional to pure water flux for all the membranes. The molecular weight cut‐offs (MWCOs) of different membranes were determined with proteins of different molecular weights and found to vary from 20–69 kDa (globular proteins) depending on the PEG and SPS content in the casting dope. Skin surface porosity of the membranes were analyzed by scanning the frozen membrane samples using scanning electron microscopy (SEM) at different magnifications. The surface porosity is in direct correlation to the MWCO derived from solute retention experiments. Copyright © 2004 John Wiley & Sons, Ltd.     

Studies on the feasibility of production of57Co by alpha bombardment of Mn and Ni targets

We have studied the feasibility of producing⁵⁷Co (271.3 d) via the⁵⁵Mn(, 2n)⁵⁷Co reaction (⁵⁵Mn–100%). The thick target yield of⁵⁷Co in the 28 to 18 MeV energy region was measured as 3.87 Ci/Ah. However, the proximity and overlap of the excitation functions for (, n), (, 2n) and (, 3n) reactions on⁵⁵Mn are such that the production of pure⁵⁷Co in high yields free of⁵⁸Co (70.8 d) and⁵⁶Co (78.8 d) has not been feasible. We have also studied a new method for ancillary production of⁵⁷Co via the reactions⁵⁸Ni(, p)⁵⁷Co and during the course of producing⁶²Zn by⁶⁰Ni(, 2n)⁶²Zn reaction. In this case the yield of⁵⁷Co of reasonable purity has been up to 1 Ci/Ah.     

Anilate Tethered Neutral Tetrahedral Pd(II) Cages Exhibiting Selective Encapsulation of Xylenes and Mesitylene

The design of porous materials for the recognition of multiple hydrocarbons is highly desirable for the energy-efficient separation and recognition of chemical feedstock. Herein, three new iso-structural porous discrete metal–organic cages of formula {[Pd₃(NiPr)₃PO]₄(R-AN)₆} (R-AN=anilate linkers) for the selective recognition of substituted aromatic hydrocarbons are reported. The tetrahedral cages 1 , 2 , and 3 containing anilate, chloranilate, and bromanilate linkers exhibited selective encapsulation of mesitylene, o-xylene, and p-xylene, respectively, over other analogous aromatic hydrocarbons. These selective encapsulations were driven by the variations in the portal diameters present at each of these cages and their interactions with the hydrocarbon guests. These observations are supported by mass spectrometry, NMR studies, and theoretical binding-energy calculations.     

Magnesium oxide nanotubes: synthesis,characterization and application as efficient recyclable catalyst for pyrazolyl 1,4-dihydropyridine derivatives

Magnesium oxide nanotubes were prepared by electrospinning technique. The nanocatalysts have been characterized by various sophisticated techniques, including XRD, SEM, and TEM. The activities of these NT catalysts are promoting pyrazolyl 1,4-dihydropyridine syntheses have been extensively investigated. Various advantages associated with these protocols simple workup procedure, short reaction times, high yields and reusability of the catalyst.     

ORGANOSTANNOXANE MOTIFS IN CAGES AND SUPRAMOLECULAR ARCHITECTURES

The reactions of n-butyl stannonic acid with(PhO) ₂ P(O)H leads to the formation of a hexameric tin cage [{(n-BuSn) ₃ (PhO) ₃ O} ₂ {HPO ₃ } ₄ ].This reaction involves an in situ P─O bond cleavage and the generation of a [HPO ₃ ] ^2? ion. A direct reaction of six equivalents of n-BuSnO(OH) acid with six equivalents of C ₆ H ₅ OH and four equivalents of H ₃ PO ₃ also leads to the formation of same cage structure. A tetranuclear organooxotin cage[(PhCH ₂ ) ₂ Sn ₂ O(O ₂ P(OH)-t-Bu) ₄ ] ₂ has been assembled by debenzylation involving the reaction of (PhCH ₂ ) ₂ SnCl ₂ ,(PhCH ₂ ) ₂ SnO·H ₂ O or (PhCH ₂ ) ₃ SnCl with two equivalents of t-BuP(O)OH ₂ . A half-cage intermediate [(PhCH ₂ ) ₂ Sn ₂ O(O ₂ P(OH)-t-Bu) ₄ ] has been detected. New organotin cations of the type [n-Bu ₂ Sn(H ₂ O) ₄ ] ²⁺[2,5-Me ₂ -C ₆ H ₃ SO ₃ ]^? ₂ and {[n-Bu ₂ Sn(H ₂ O) ₃ LSn(H ₂ O) ₃ (n-Bu) ₂ ] ²⁺[1,5-(SO ₃ ) ₂ -C ₁₀ H ₆ ] ^2?} have been obtained in the reactions of n-Bu ₂ SnO or (n-Bu ₃ Sn) ₃ O with 2,5-dimethyl sulfonic acid and 1,5-naphthalene disulfonic acid respectively. These organotin cations form interesting supramolecular structures in the solid state as a result of O─H─···O hydrogen bonding.     

Atomically flat single terminated oxide substrate surfaces

Scientific interest in atomically controlled layer-by-layer fabrication of transition metal oxide thin films and heterostructures has increased intensely in recent decades for basic physics reasons as well as for technological applications. This trend has to do, in part, with the coming post-Moore era, and functional oxide electronics could be regarded as a viable alternative for the current semiconductor electronics. Furthermore, the interface of transition metal oxides is exposing many new emergent phenomena and is increasingly becoming a playground for testing new ideas in condensed matter physics. To achieve high quality epitaxial thin films and heterostructures of transition metal oxides with atomically controlled interfaces, one critical requirement is the use of atomically flat single terminated oxide substrates since the atomic arrangements and the reaction chemistry of the topmost surface layer of substrates determine the growth and consequent properties of the overlying films. Achieving the atomically flat and chemically single terminated surface state of commercially available substrates, however, requires judicious efforts because the surface of as-received substrates is of chemically mixed nature and also often polar. In this review, we summarize the surface treatment procedures to accomplish atomically flat surfaces with single terminating layer for various metal oxide substrates. We particularly focus on the substrates with lattice constant ranging from 4.00 Å to 3.70 Å, as the lattice constant of most perovskite materials falls into this range. For materials outside the range, one can utilize the substrates to induce compressive or tensile strain on the films and explore new states not available in bulk. The substrates covered in this review, which have been chosen with commercial availability and, most importantly, experimental practicality as a criterion, are KTaO₃, REScO₃ (RE = Rare-earth elements), SrTiO₃, La_0.18Sr_0.82Al_0.59Ta_0.41O₃ (LSAT), NdGaO₃, LaAlO₃, SrLaAlO₄, and YAlO₃. Analyzing all the established procedures, we conclude that atomically flat surfaces with selective A- or B-site single termination would be obtained for most commercially available oxide substrates. We further note that this topmost surface layer selectivity would provide an additional degree of freedom in searching for unforeseen emergent phenomena and functional applications in epitaxial oxide thin films and heterostructures with atomically controlled interfaces.