Catalytic, asymmetric synthesis of α,α-disubstituted amino acids

Copper(salen) complex 1 has been found to catalyse the asymmetric alkylation of enolates derived from a variety of amino acids. There is a clear relationship between the size of the side chain in the substrate and the enantioselectivity of the process, so that the enantioselectivity decreases in the order alanine>aminobutyric acid>allylglycine>leucine>phenylalanine>valine. A transition state model which accounts for the influence of the size of the side chain on the enantioselectivity of the reactions is presented.     

Integer programming formulations of vehicle routing problems

Various mathematical formulations are available for situations represented by vehicle routing problems. The assignment-based integer programming formulations of these problems are more common and easy to understand. Such formulations are discussed in this paper and a much simpler formulation for the vechicle routing problem is presented for the case, when all the vehicles have the same load capacity and maximum allowable cost per route.     

Thermal and electrical studies of some polychelates

Polychelates of Mn(II), Fe(II), Co(II), Ni(II), and Cu(II) with 4,4′-dihydroxy-3,3′-diacetylbiphenyl-dithioxamide (DDBDO) have been prepared. Their structures were determined by visible reflectance spectroscopy and magnetic measurements in conjunction with thermogravimetric and IR measurements. Elemental analysis indicates a 1∶1 metal-ligand stoichiometry and the association of water molecules with the central metal. The decomposition temperature of the chelates is in the order Ni(II)>Fe(II)>Co(II)>Mn(II)>Cu(II). Thermal activation energies (E _a ), calculated with the help of Freeman-Carroll and Sharp-Wentworth methods, are in agreement with each other. The polychelates were found to be semiconductive, and the activation energy obtained from semiconducting behavior follows the order Co(II)>Ni(II)>Fe(II)>Cu(II)>Mn(II). The probable structure, such as six coordinated octahedral for Mn(II) and Fe(II) polychelates and four coordinated square planar for Co(II), Ni(II), and Cu(II) polychelates, have been suggested.     

A comparative study on aqualuminescence,chemical effects and photoannealing of γ-irradiated NaCl and K2SO4

Dissolution of -irradiated sodium chloride and potassium sulphate powders in pure water and aqueous sodium nitrate solution results in the emission of light in the former, and the formation of nitrite in the latter case. Appropriate mechanisms have been suggested for the luminescence and NO ₂ ^– formation in the light of the known radiolytic products formed in the salts during the irradiation. The photoannealing of the irradiated sodium chloride under the influence of visible light and K₂SO₄ by visible ultraviolet and laser lights has been studied by monitoring the changes in the NO ₂ ^– yield with annealing times. The observed changes in the nitrite yields have been correlated with the bleaching of the radiolytic products during the photoannealing of these salts.     

Monoliths for the purification of whey protein-dextran conjugates

Proteins conjugated to neutral biopolymers are of keen interest to the food and pharmaceutical industries. Conjugated proteins are larger and more charge shielded than un-reacted proteins, making purification difficult using conventional beaded chromatographic supports because of slow mass transfer rates, weak binding, and viscous solutions. Past methods developed for pharmaceuticals are unsuitable for foods. In this work, a food-grade whey protein-dextran conjugate was purified from a feed solution also containing un-reacted protein and dextran using either a column packed with 800 mL of a beaded support that was specifically designed for purification of conjugated proteins or an 8 mL tube monolith. The monolith gave a similar dynamic binding capacity as the beaded support (4-6 g/L), at a 42-fold greater mass productivity, and 48-fold higher flow rate, albeit at somewhat lower conjugate purity. Performance of the monolith did not depend on flow rate. In conclusion, monoliths were found to be well suited for the purification of whey protein-dextran conjugates.     

Electrical characteristics of etched ion-tracks in polyimide filled with silver nanoparticles

Silicon ions, of energy 150?MeV and fluence ～10¹²?ions/cm², were used to register latent tracks in 40?µm thick polyimide samples. Different sizes of tracks were obtained by etching the ion irradiated polyimide samples, in chemical solutions, by varying the temperature and etching period. Silver nanoparticles were diffused into the etched tracks by immersing the polyimide samples in silver solution and then irradiating with 6.5?MeV electrons at different fluences varying from 1?×?10¹⁵ to 5?×?10¹⁵?cm^?2. Results of morphological and elemental analysis, carried out by Scanning Electron Microscopy and Energy Dispersive X-ray. Analysis revealed that the conical tracks could be fully filled with silver nanoparticles at electron fluence of 5?×?10¹⁵?cm^?2. The minimum d. c. resistance of an array of tracks, filled with silver nanoparticles and measured across the polyimide film, was orders of magnitude higher as compared to that of silver wires of equivalent sizes connected in parallel. In addition, these silver nanoparticles filled tracks exhibited rectifying I–V behavior and frequency dependent a. c. resistance, characteristic of metal–polymer nano-composites. Possible mechanisms have been discussed, which can justify the asymmetric current–voltage characteristics in such nano-composites.     

Synthesis,Characterization, and Catalytic Activity of a Cubic [Mo3S4Pd] Cluster Bearing Bulky Cyclopentadienyl Ligands

A cubic metal-sulfur cluster containing three Mo ions and a Pd ion, [Cp^SiEt3₃Mo₃S₄Pd]Cl ( Mo₃Pd , Cp^SiEt3=C₅Me₄SiEt₃), was synthesized by the incorporation of the Pd ion into a Mo₃S₄ cluster [Cp^SiEt3₃Mo₃S₄] ( Mo₃ ). Mo₃Pd was characterized by ¹H NMR, UV-vis, X-ray crystallography, and cyclic voltammetry measurements. The electrochemical measurements demonstrated reversible one- and two-electron reduction processes for Mo₃Pd , which suggested potential catalytic activity for two-electron substrate reductions such as hydrogen evolution reaction. Controlled potential electrolysis in the presence of Mo₃Pd and trifluoroethanol in THF solvent displayed H₂ formation with a constant current over 60 min. The amount of generated H₂ by Mo₃Pd was two times higher than Mo₃ , indicating the catalytic activity facilitated by the Pd center. The mechanism of the catalytic cycle was determined by density functional theory.     

Analogue of Kida's formula for certain strongly admissible extensions

We study the Iwasawa theory of elliptic curves over certain infinite (non-commutative) p-adic Galois-Lie extensions. In particular, we consider the analogue of the classical Iwasawa λ-invariant and Kida's formula for the dual Selmer group.