The effect of functionalization on structure and electrical conductivity of multi-walled carbon nanotubes

Nanosized powders of Ti-Nb oxide core-shell nanocrystals with atomic ratios of Nb/Ti = 0.11, 0.25, and 0.38 have been prepared by two preparation routes. The first route was co-precipitation, followed by␣annealing, using NbCl₅ as a source of Nb. The second route was coating of pure TiO₂ nanocrystals by Nb-isopropoxide in liquid medium, followed by impregnation of the Nb into the nanoparticles by annealing. Both methods yielded anatase nanocrystals with a Nb-rich shell and a core, which had much lower Nb loadings. The anatase structure solid solution (with Nb incorporated) was stable under annealing up to 760°C. The particle size remained within the nanometric scale (<50 nm) under heat-treatment up to 760°C. It has been shown that the fabricated powders can be redispersed in aqueous media by simple ultrasound treatment, resulting in nanosized dispersions. Using a variety of analytical techniques, including depth profiling of single nanocrystallites by AES combined with sputtering by Ar ions, the mechanism of the core-shell structure creation was studied. It is proposed that the formation of the core-shell structure is governed by solubility limitations in the co-precipitation route and by solubility and diffusion limitations in the coating-incorporation route.     

Asymmetric synthesis of 4'-ethoxy-2',3'-didehydro-2',3'-dideoxynucleosides by palladium-catalyzed kinetic discrimination between the corresponding diastereoisomeric lactol acetates

4'-Substituted nucleoside analogues have been synthesized using palladium-catalyzed asymmetric allylic amination conditions. A kinetic discrimination between the diastereomeric lactol acetates (3) produced the desired aminated products (6a-d) and recovered acetate (alpha-3) in high yields and <97:3 diastereoselectivity. Epimerization of the recovered lactol acetate (alpha-3) produced a 60:40 alpha/beta mixture of (3), which could be resubjected, in principle, to the palladium-catalyzed asymmetric allylic amination conditions.     

Microcrystalline and three-dimensional network structure of plasticized poly(vinyl chloride)

Three-dimensional networks can be formed in plasticized poly(vinyl chloride) by chain entanglements and crystallites introduced in the system during the fusion and annealing processes. The fusion conditions influence the mechanical stability of the plasticized polymers, by establishing regions where one-phase systems are observed. During annealing at temperatures of between 170 and 190 °C, for up to 9 minutes, maximum degree of crystallinity of 0.079 was detected for samples plasticized with 20 wt% di-2-ethyl-hexyl-phthalate. Experimental analysis of mechanical properties and analysis of stress relaxation experiments showed that rubber elasticity theories could be applied with some approximation to plasticized PVC to analyze the structure of the three-dimensional networks formed.     

The effect of rate of stimulation on perception of spectral shape by cochlear implantees

The effect of rate of stimulation on spectral shape perception was measured in six users of the Nucleus CI24 cochlear implant. Three spectral shapes were created by using three profiles of current across seven electrode positions. Each current profile was replicated in three stimuli that interleaved stimulus pulses across the seven electrodes with cycle rates (rate per electrode) of 450, 900, and 1800 Hz. The stimulus space resulting from a multidimensional scaling experiment showed a clear dimension related to the rate of stimulation that was orthogonal to the dimension related to the spectral shapes. A second experiment was performed with the same subjects to investigate whether the perceptual dimension related to rate in Experiment 1 could be attributed to different perceptual flatness of the profiles at different rates. In Experiment 2, the rate of stimulation was fixed at 900 Hz and three profiles were created for each spectral shape that differed in flatness. This experiment did not, however, result in an independent perceptual dimension related to the flatness of the profile. In conclusion, rate of stimulation provided an independent perceptual dimension in the multiple-electrode stimuli, in spite of the rates being not discriminable or barely discriminable in single-electrode stimulation.     

Versatile and facile synthesis of diverse semisynthetic tetracycline derivatives via Pd-catalyzed reactions

A diverse collection of tetracycline derivatives has been synthesized utilizing Heck, Suzuki, and other palladium-coupling reactions via tetracycline arenediazonium and iodoarene salts. Large numbers of tetracyclines are now possible via these reactions, including numerous upper periphery derivatives of doxycycline, minocycline, sancycline, and methacycline modified at positions C7, C9, and C6-C13 on the tetracycline naphthacene ring. Application of palladium-coupling reactions to the tetracyclines has yielded new tetracycline classes with differing structural attributes, greatly increasing the structural diversity of this family of antibiotics, one of the last of the early antibiotic families to be expanded by organic and medicinal chemistry.     

Hypochlorite-mediated fragmentation of hyaluronan, chondroitin sulfates, and related N-acetyl glycosamines: evidence for chloramide intermediates, free radical transfer reactions, and site-specific fragmentation

Myeloperoxidase released from activated phagocytes reacts with H(2)O(2) in the presence of chloride ions to give hypochlorous acid. This oxidant has been implicated in the fragmentation of glycosaminoglycans, such as hyaluronan and chondroitin sulfates. In this study it is shown that reaction of HOCl with glycosaminoglycans and model compounds yields chloramides derived from the N-acetyl function of the glycosamine rings. The results of EPR spin trapping and product studies are consistent with the formation of amidyl radicals from these chloramides via both metal ion-dependent and -independent processes. In the case of glycosaminoglycan-derived amidyl radicals, evidence has been obtained in studies with model glycosides that these radicals undergo rapid intramolecular abstraction reactions to give carbon-centered radicals at C-2 on the N-acetyl glycosamine rings (via a 1,2-hydrogen atom shift) and at C-4 on the neighboring uronic acid residues (via 1,5-hydrogen atom shifts). The C-4 carbon-centered radicals, and analogous species derived from model glycosides, undergo pH-independent beta-scission reactions that result in glycosidic bond cleavage. With N-acetyl glucosamine C-1 alkyl glycosides, product formation via this mechanism is near quantitative with respect to chloramide loss. Analogous reactions with the glycosaminoglycans result in selective fragmentation at disaccharide intervals, as evidenced by the formation of "ladders" on gels; this selectivity is less marked under atmospheric oxygen concentrations than under anoxic conditions, due to competing peroxyl radical reactions. As the extracellular matrix plays a key role in mediating cell adhesion, growth, activation, and signaling, such HOCl-mediated glycosaminoglycan fragmentation may play a key role in disease progression and resolution, with the resulting fragments modulating the magnitude and quality of the immune response in inflammatory conditions.