Macrocyclic polycther sulfide syntheses. The preparation of thia-crown-5, 6 and 7 compounds

Macroeyclic polyether sulfides have been prepared by reacting an oligoethylene glycol dichloride with a dimercaptan or sodium sulfide as reported in a previous paper (6). The following new compounds were prepared: 1,4,7-trithia(15-crown-5) (1); 1,4,10-trithia(15-crown-5) (II): 1,4,7,10-tetrathia(15-crown-5) (III); I-thia(18-crown-6) (IV); 1,4-dithia(18-crown-6) (V); 1,7-dithia(18-crown-6) (VI); 1,4,7-trithia(18-crown-6) (VII); 1,7-dithia(21-crown-7) (VIII); and 1,4,7-trithia(21-crown-7) (IX). The melting points of these and previously reported thia-crown compounds correlate with their structures. X-ray analyses of two thia-crown compounds indicate that the large sulfur atoms are directed away from the center of the ring.     

Octahedral cobalt(III) complexes of the chloropentammine type. XXVII. Effects of Methyl Substituents on reactivities of the cis-chloro-n-propylaminebis(ethylenediamine)-cobalt(III) cation

Salts of one isomeric form of the chloro-n-butylamine-, chloro-iso-butyl-amine- and chloro-sec-butylamine-bis(ethylenediamine)cobalt(III) cations have been prepared and characterised to have a cis-configuration (IR and VIS spectroscopy). Rate constants for their spontaneous aquation, mercury(II)-induced aquation and base hydrolysis have been determined and the activation parameters calculated. The results are compared with data obtained for the n-propylamine complex with a view to investigate the effects of methyl (α, β, γ) substituents on reactivities. The rate-determining dissociation of the outgoing group (Cl^? or HgCl⁺) takes place via either a square-pyramidal or a trigonal-bipyramidal intermediate, depending on whether the activation entropy is negative or positive.     

Solution properties of polyoxymethylene

Light scattering and viscosity have been measured at 25°C. for dilute solutions of six unfractionated polyoxymethylene samples in the mixed solvent hexafluoroacetone–water (mole ratio 1/1.7) slightly buffered with triethylamine. Dialysis equilibrium through porous Vycor glass thimbles indicates that the polymer is strongly solvated by the hydrate (CF₃)₂C(OH)₂, and this must be taken into account in evaluating weight-average molecular weights from the light-scattering data. Over the molecular weight range 23,000–185,000, the intrinsic viscosities (in deciliter per gram) follow the relation The corresponding unperturbed dimensions are σ = 2.3 ± 0.2 or r₀²/nl² = 10.5 ± 1.5.     

Carbon anode materials from polysiloxanes for lithium ion batteries

Three kinds of silicon-containing disordered carbons have been prepared by pyrolysis of polysiloxanes with different amounts of phenyl side groups. X-ray powder diffraction, X-ray photoelectron spectroscopy and electrochemical capacity measurements were performed to study their behaviors. Graphite crystallites, micropores, and silicon species affect their electrochemical performances. All of them present high reversible capacities, >372 mAh/g. Since the graphite crystallites are very small, they contribute very little to reversible capacity. The number of micropores produced by gas emission during the heat-treatment process decides whether they exhibit reversible capacity. Si mainly exists in the form C–Si–O and influences the irreversible capacity. There is no evident capacity fading in the first ten cycles, indicating promising properties for these disordered carbons.     

Palladium-catalyzed C-O bond formation: direct synthesis of phenols and aryl/alkyl ethers from activated aryl halides

A simple and efficient palladium-catalyzed carbon-oxygen bond formation is reported. The palladium-tri-tert-butylphosphine complex was found to be effective in converting haloarenes to corresponding substituted phenols. This methodology offers a direct transformation of aryl halides to phenols, as well as the straightforward application to generate a wide variety of diaryl or alkyl/aryl ethers.     

Broadband rotational resonance in solid state NMR spectroscopy

A new technique for restoring nuclear magnetic dipole-dipole couplings under magic-angle spinning (MAS) in solid state nuclear magnetic resonance (NMR) spectroscopy is described and demonstrated. In this technique, called broadband rotational resonance (BroBaRR), the coupling between a pair of nuclear spins with NMR frequency difference close (but not necessarily equal) to the MAS frequency is restored by the application of a train of weak radio-frequency pulses at a carrier frequency close to the average of the two NMR frequencies. Phase or amplitude modulation of the pulse train at half the MAS frequency splits the carrier into sidebands close to the two NMR frequencies. The pulse train then removes offsets from the exact rotational resonance condition, leading to dipolar recoupling over a bandwidth controlled by the amplitude of the pulse train. (13)C NMR experiments on uniformly (15)N,(13)C-labeled L-valineHClH(2)O powder validate the theoretical analysis. BroBaRR will be useful in studies of molecular structures by solid state NMR, for example in the detection of long-range couplings between carbons in uniformly labeled organic and biological materials.     

Quinazolines and 1,4-benzodiazepines. XLVI. Photochemistry of nitrones and oxaziridines

The cyclic nitrones 7-chloro-1,3-dihydro-5-phenyl-2H-1,4-benzodiazepin-2-one 4-oxide ( 5a ) and 1,3-dihydro-7-methylthio-5-phenyl-2H-1,4-benzodiazepin-2-one 4-oxide ( 5b ) are photoisomerized to readily isolable oxaziridines, 7-chloro-4,5-epoxy-5-phenyl-1,3,4–5-tetrahydro-2H-1,4-benzodiazepin-2-one ( 6a ) and 4,5-epoxy-5-phenyl-1,3,4,5-tetrahydro-7-methylthio-2H-1,4-benzo-diazepin-2-one ( 6b ). Oxaziridine 6b upon further irradiation gave ring expansion and ring contraction products, 4,6-dihydro-2-phenyl-9-methylthio-5H-1,3,6-benzoxadiazocin-5-one ( 7b ) and 4-benzoyl-3,4-dihydro-6-methylthioquinoxalin-2(1H)-one ( 8b ) respectively. The ring contraction product, 4-benzoyl-6-chloro-3,4-dihydroquinoxalin-2(1H)-one ( 8a ), was obtained from irradiation of oxaziridine 6a .     

Sorption of 241Am by Aspergillus nigerspore and hyphae

Biosorption of ²⁴¹Am by a fungus A. niger, including the spore and hyphae, was investigated. The preliminary results showed that the adsorption of ²⁴¹Am by the microorganism was efficient. More than 96% of the total ²⁴¹Am could be removed from ²⁴¹Am solutions of 5.6-111 MBq/l (C _o) by spore and hyphaeof A. niger, with adsorbed ²⁴¹Am metal (Q) of 7.2-142.4 MBq/g biomass, and 5.2-106.5 MBq/g, respectively. The biosorption equilibrium was achieved within 1 hour and the optimum pH range was pH 1-3. No obvious effects on ²⁴¹Am adsorption by the fungus were observed at 10-45 °C, or in solutions containing Au³⁺ or Ag⁺, even 2000 times above the ²⁴¹Am concentration. The ²⁴¹Am biosorption by the fungus obeys the Freundlich adsorption equation. There was no significant difference between the adsorption behavior of A. nigerspore and hyphae. This revised version was published online in July 2006 with corrections to the Cover Date.     

Kinetic theory of reacting systems

In this paper transport processes of reacting systems are investigated, based on the Boltzmann equations. The Boltzmann equations are solved by means of Grad's moment method to thirteen moments and some formal results are obtained for transport properties. It is shown that the rate coefficients are quadratic functions of hydrodynamic fluxes and are in the form

where

are the scalar moments associated with the reaction and q, J, Π are heat flux, material flux and traceless symmetric stress tensor. k⁽⁰⁾_i is the usual local equilibrium formula for reaction rate constant. Iterative solutions for the equations of change for

, q, J and Π are obtained from which transport coefficients are calculated for the reacting system. It is shown that the solutions, when specialized to nonreacting mixtures, lead to results for the transport coefficients which are exactly in agreement with the Chapman-Enskog theory results. The modifications of the transport coefficients due to reactions are obtained from the iterative solutions and the bracket integrals necessary for their calculations are explicitly given in an appendix.     

Biosorption of americium-241 by Saccharomyces cerevisiae

The biosorption of radionuclide ²⁴¹Am from solution by Saccharomyces cerevisiae (S. cerevisiae), and the effects of experimental conditions on the adsorption were investigated. The preliminary results showed thatS. cerevisiae is a very efficient biosorbent. An average of more than 99% of the total ²⁴¹Am could be removed by S. cerevisiae of 2.1 g/l (dry weight) from ²⁴¹Am solutions of 17.54–4386.0 mg/l (2.22 MBq/l–555 MBq/l) with adsorption capacities of 7.45–1880.0 mg/g biomass (dry weight) (0.94 MBq/g–237.9 MBq/g). The adsorption equilibrium was achieved within 1 hour and the optimum pH ranged 1–3. No significant differences on ²⁴¹Am adsorption were observed at 10–45 °C, or in solutions containing Au³⁺ or Ag⁺, even 2000 times above ²⁴¹Am concentration. The relationship between concentrations and adsorption capacities of ²⁴¹Am indicated the biosorption process should be described by the Freundlich adsorption isotherm.