Reversible Formation of a Planar Chiral Ferrocenylboroxine and Its Supramolecular Structure

The boronic acid (pS)-1,2-NpFcB(OH)(2) (1) was obtained by treatment of the lithiated species (pS)-1,2-NpFcLi with B(O(i)Pr)(3), followed by acidic workup; subsequent dehydration gave the enantiomerically pure boroxine [(pS)-1,2-NpFcBO](3) (2) in 49% isolated yield. Multinuclear and 2D NMR spectroscopies, single-crystal X-ray diffraction, and elemental analysis served to confirm the structure of 2. In the solid-state structure, all three of the naphthyl groups point in one direction and all of the ferrocenyl moieties are placed on the opposite face of the boroxine ring, which is also the preferred conformation in solution according to a (1)H, (1)H-NOESY experiment. Cyclic voltammetry revealed three separate reversible oxidation events, which suggests significant communication between the ferrocenyl moieties. These redox processes experience a cathodic shift upon addition of 4-dimethylaminopyridine (DMAP) as a Lewis base. The six-membered ring is opened upon treatment with hot CHCl(3)/MeOH to form the methoxy species (pS)-1,2-NpFcB(OH)(OMe) (3), which can be converted back to the cycle 2 by dissolution in wet CHCl(3), followed by column chromatography on silica gel.

Geochemical behaviour of dissolved trace elements in a monsoon-dominated tropical river basin, Southwestern India

The study presents a 3-year time series data on dissolved trace elements and rare earth elements (REEs) in a monsoon-dominated river basin, the Nethravati River in tropical Southwestern India. The river basin lies on the metamorphic transition boundary which separates the Peninsular Gneiss and Southern Granulitic province belonging to Archean and Tertiary-Quaternary period (Western Dharwar Craton). The basin lithology is mainly composed of granite gneiss, charnockite and metasediment. This study highlights the importance of time series data for better estimation of metal fluxes and to understand the geochemical behaviour of metals in a river basin. The dissolved trace elements show seasonality in the river water metal concentrations forming two distinct groups of metals. First group is composed of heavy metals and minor elements that show higher concentrations during dry season and lesser concentrations during the monsoon season. Second group is composed of metals belonging to lanthanides and actinides with higher concentration in the monsoon and lower concentrations during the dry season. Although the metal concentration of both the groups appears to be controlled by the discharge, there are important biogeochemical processes affecting their concentration. This includes redox reactions (for Fe, Mn, As, Mo, Ba and Ce) and pH-mediated adsorption/desorption reactions (for Ni, Co, Cr, Cu and REEs). The abundance of Fe and Mn oxyhydroxides as a result of redox processes could be driving the geochemical redistribution of metals in the river water. There is a Ce anomaly (Ce/Ce*) at different time periods, both negative and positive, in case of dissolved phase, whereas there is positive anomaly in the particulate and bed sediments. The Ce anomaly correlates with the variations in the dissolved oxygen indicating the redistribution of Ce between particulate and dissolved phase under acidic to neutral pH and lower concentrations of dissolved organic carbon. Unlike other tropical and major world rivers, the effect of organic complexation on metal variability is negligible in the Nethravati River water.

Oxygen-participated electrochemistry of new lithium-rich layered oxides Li3MRuO5 M = Mn, Fe)

We describe the synthesis, crystal structure and lithium deinsertion-insertion electrochemistry of two new lithium-rich layered oxides, Li3MRuO5 (M = Mn, Fe), related to rock salt based Li2MnO3 and LiCoO2. The Li3MnRuO5 oxide adopts a structure related to Li2MnO3 (C2/m) where Li and (Li0.2Mn0.4Ru0.4) layers alternate along the c-axis, while the Li3FeRuO5 oxide adopts a near-perfect LiCoO2 (R (3) over barm) structure where Li and (Li0.2Fe0.4Ru0.4) layers are stacked alternately. Magnetic measurements indicate for Li3MnRuO5 the presence of Mn3+ and low spin configuration for Ru4+ where the itinerant electrons occupy a pi*-band. The onset of a net maximum in the chi vs. T plot at 9.5 K and the negative value of the Weiss constant (theta) of -31.4 K indicate the presence of antiferromagnetic superexchange interactions according to different pathways. Lithium electrochemistry shows a similar behaviour for both oxides and related to the typical behaviour of Li-rich layered oxides where participation of oxide ions in the electrochemical processes is usually found. A long first charge process with capacities of 240 mA h g(-1) (2.3 Li per f.u.) and 144 mA h g(-1) (1.38 Li per f.u.) is observed for Li3MnRuO5 and Li3FeRuO5, respectively. An initial sloping region (OCV to ca. 4.1 V) is followed by a long plateau (ca. 4.3 V). Further discharge-charge cycling points to partial reversibility (ca. 160 mA h g(-1) and 45 mA h g(-1) for Mn and Fe, respectively). Nevertheless, just after a few cycles, cell failure is observed. X-ray photoelectron spectroscopy (XPS) characterisation of both pristine and electrochemically oxidized Li3MRuO5 reveals that in the Li3MnRuO5 oxide, Mn3+ and Ru4+ are partially oxidized to Mn4+ and Ru5+ in the sloping region at low voltage, while in the long plateau, O2- is also oxidized. Oxygen release likely occurs which may be the cause for failure of cells upon cycling. Interestingly, some other Li-rich layered oxides have been reported to cycle acceptably even with the participation of the O2- ligand in the reversible redox processes. In the Li3FeRuO5 oxide, the oxidation process appears to affect only Ru (4+ to 5+ in the sloping region) and O2- (plateau) while Fe seems to retain its 3+ state.

Edge-sharing bioctahedral diruthenium(III) complexes containing methoxy and carboxylate bridges:x-ray structures, redox behavior, and core stability

Edge-sharing bioctahedral (ESBO) complexes [Ru-2(OMe)(O2CC6H4-p-X)3(1-MeIm)(4)](ClO4)2 (X = OMe (1a), Me (1b)) and [Ru-2(O2CC6H4-P-X)(4)(1-MeIm)(4)](ClO4)(2) (X = OMe (2a), Me (2b)) are prepared by reacting Ru2Cl(O(2)CR)(4) with 1-methylimidazole (1-MeIm) in methanol followed by treatment with NaClO4. Complex 2a and the PF6- salt (1a') of 1a have been structurally characterized. Crystal data for 1a.1.5MeCN. 0.5Et(2)O: triclinic, P (1) over bar, a = 13.125(2) Angstrom, b = 15.529(3) Angstrom, c 17.314(5) Angstrom, a; 67.03(2)degrees, beta 68.05(2)degrees, gamma = 81.38(1)degrees, V 3014(1) Angstrom(3), Z = 2. Crystal data for 2a: triclinic, P (1) over bar, a 8.950(1) Angstrom, b = 12.089(3) Angstrom, c = 13.735(3) Angstrom, alpha 81.09(2)degrees, beta = 72.27(1)degrees, gamma = 83.15(2)degrees, V = 1394(1) Angstrom(3), Z = 1. The complexes consist of a diruthenium(III) unit held by two monoatomic and two three-atom bridging ligands. The 1-MeIm ligands are at the terminal sites of the [Ru-2(mu-L)(eta(1):mu-O(2)CR)(eta(1):eta(1):mu-O(2)CR)(2)](2+) core having a Ru-Ru single bond (L = OMe or eta(1)-O(2)CR). The Ru-Ru distance and the Ru-O-Ru angle in the core of 1a' and 2a are 2.49 Angstrom and similar to 76 degrees. The complexes undergo one-electron oxidation and reduction processes in MeCN-0.1 M TBAP to form mixed-valence diruthenium species with Ru-Ru bonds of orders 1.5 and 0.5, respectively.

Synthesis, redox and electrochemical properties of new anthraquinone-attached micelle- and vesicle-forming cationic amphiphiles

Three new cationic amphiphiles bearing anthraquinone moieties at the polar headgroup region were synthesized, The single-chain amphiphile, N,N-dimethyl-N-octadecyl-N-(9,10-dihydro dioxoanthracen-2-ylmethyl)ammonium bromide 1, in the presence of cetyltrimethylammonium bromide upon dispersion in water gave co-micellar aggregates containing covalently attached anthraquinone residues at the polar aqueous interfaces. The other two double-chain amphiphiles, N,N-dioctadecyl-N-methyl-N-(9,10-dihydro-9,10-dioxoanthracen-2-ylmethyl)ammonium bromide 2 and N,N-dimethyl-N-(1,2-bispalmitoyloxypropanyl)-N-(9,10-dihydro-9,10-dioxanthracen-2-ylmethyl)ammonium bromide 3, however, on dispersion in aqueous media produced vesicular aggregates. The critical temperatures for the gel to liquid-crystalline-like phase transition processes for the vesicular systems were determined by following temperature-dependent changes in the ratios of keto-enol tautomeric forms of benzoylacetanilide doped within respective. vesicular assemblies. The redox chemistry of the these supramolecular assemblies was also studied by following the time-dependent changes in the ITV-VIS absorption spectroscopy in the presence of exogenous reducing or oxidizing agents, Electrochemical studies using glassy carbon electrodes reveal that redox-active amphiphiles adsorb on to the glassy carbon surfaces to form electroactive deposits when dipped into aqueous suspensions of either of these aggregates irrespective of the micellar or vesicular nature of the dispersions.

Electron transfer amongst flavo- and hemo-proteins: diffusible species effect the relay processes, not protein-protein binding

Hitherto, electron transfer (ET) between redox proteins has been deemed to occur via donor-acceptor binding, and diffusible reactive species are considered as deleterious side-products in such systems. Herein, ET from cytochrome P450 reductase (CPR, an animal membrane flavoprotein) and horseradish peroxidase (HRP, a plant hemoprotein) to cytochrome c (Cyt c, a soluble animal hemoprotein) was probed under diverse conditions, using standard assays. ET in the CPR-Cyt c system was critically inhibited by cyanide and sub-equivalent levels of polar one-electron cyclers like copper ions, vitamin C/Trolox and superoxide dismutase. In the presence of lipids, inhibition was also afforded by amphipathic molecules vitamin E, palmitoyl-vitamin C and the membrane hemoprotein, cytochrome b(5). Such nonspecific inhibition (by diverse agents in both aqueous and lipid phases) indicated that electron transfer/relay was effected by small diffusible agents, whose lifetimes are shortened by the diverse radical scavengers. When CPR was retained in a dialysis membrane and Cyt c presented outside in free solution, ET was still observed. Further, HRP (taken at nM levels) catalyzed oxidation of a phenolic substrate was significantly inhibited upon the incorporation of sub-nM levels of Cyt c. The findings imply that CPR-Cyt c or HRP-Cyt c binding is not crucial for ET. Further, fundamental quantitative arguments (based on diffusion/collision) challenge the erstwhile protein-protein binding-assisted ET hypothesis. It is proven beyond reasonable doubt that mobile and diffusible electron carriers (ions and radicals) serve as ``redox-relay agents'' in the biological ET models/setup studied.

Study of the processes occurring when sputtering YBa2Cu3O7-x in pure oxygen

The sputter deposition of YBa2Cu3O7-x in a de-diode was performed in pure oxygen medium and an optical spectroscopic study of the resultant discharge revealed strong emissions from both metal atoms and oxygen ions. Emission intensities were studied in pressure range from 0.5 to 3 mbar, with substrate temperatures from 150 to 850 degrees C. Raising the substrate temperature to 850 degrees C increased the number of positive ions and excited neutral atoms. Raising the pressure decreased the emission intensities of excited neutral and ionic species. The results have been compared with those obtained from Langmuir probe measurements. The rise in emission intensities of excited neutrals and ions with temperature suggested the possibility of chemically enhanced physical sputtering of YBa2Cu3O7-x. The effect of process conditions on film composition and quality is also discussed.

Influence of friction during forming processes-a study using a numerical simulation technique

Friction has an important influence in metal forming operations, as it contributes to the success or otherwise of the process. In the present investigation, the effect of friction on metal forming was studied by simulating compression tests on cylindrical Al-Mg alloy using the finite element method (FEM) technique. Three kinds of compression tests were considered wherein a constant coefficient of friction was employed at the upper die-work-piece interface. However, the coefficient of friction between the lower die-work-piece interfaces was varied in the tests. The simulation results showed that a difference in metal flow occurs near the interfaces owing to the differences in the coefficient of friction. It was concluded that the variations in the coefficient of friction between the dies and the work-piece directly affect the stress distribution and shape of the work-piece, having implications on the microstructure of the material being processed.

Thermal Degradation Processes in Poly(xylylene sulfides) Investigated by Comparative Direct Pyrolysis MS and Flash Pyrolysis GC/MS Experiments

The thermal degradation processes of two sulfur polymers, poly(xylylene sulfide) (PXM) and poly(xylylene disulfide) (PXD), were investigated in parallel by direct pyrolysis mass spectrometry (DPMS) and flash pyrolysis GC/MS (Py-GC/MS). Thermogravimetric data showed that these polymers decompose with two separate steps in the temperature ranges of 250-280 and 600-650 degrees C, leaving a high amount of residue (about 50% at 800 degrees C). The pyrolysis products detected by DPMS in the first degradation step of PXM and PXD were terminated by three types of end groups, -CH3, -CH2SH, and -CH=S, originating from thermal cleavage reactions involving a series of homolytic chain scissions followed by hydrogen transfer reactions, generating several oligomers containing some intact xylylene sulfide repeating units. The presence of pyrolysis compounds containing some stilbene-like units in the first degradation step has also been observed. Their formation has been accounted for with a parallel cleavage involving the elimination of H2S from the PXM main chains. These unsaturated units can undergo cross-linking at higher temperatures, producing the high amount of char residue observed. The thermal degradation compounds detected by DPMS in the second decomposition step at about 600-650 degrees C were constituted of condensed aromatic molecules containing dihydrofenanthrene and fenanthrene units. These compounds might be generated from the polymer chains containing stilbene units, by isomerization and dehydrogenation reactions. The pyrolysis products obtained in the Py-GC/MS of PXM and PXD at 610 degrees C are almost identical. The relative abundance in the pyrolysate and the spectral properties of the main pyrolysis products were found to be in generally good agreement with those obtained by DPMS. Polycyclic aromatic hydrocarbons (PAHs) were also detected by Py-GC/MS but in minor amounts with respect to DPMS. This apparent discrepancy was due to the simultaneous detection of PAHs together with all pyrolysis products in the Py-GC/MS, whereas in DPMS they were detected in the second thermal degradation step without the greatest part of pyrolysis compounds generated in the first degradation step. The results obtained by DPMS and PSI-GC/MS experiments showed complementary data for the degradation of PXM and PXD and, therefore, allowed the unequivocal formulation of the thermal degradation mechanism for these sulfur-containing polymers.

Pt metal-CeO2 interaction: Direct observation of redox coupling between Pt-0/Pt2+/Pt4+ and Ce4+/Ce3+ states in Ce0.98Pt0.02O2-delta catalyst by a combined electrochemical and x-ray photoelectron spectroscopy study

Pt ions-CeO2 interaction in Ce1-xPtxO2-delta (x=0.02) has been studied for the first time by electrochemical method combined with x-ray diffraction and x-ray photoelectron spectroscopy. Working electrodes made of CeO2 and Ce0.98Pt0.02O2-delta mixed with 30% carbon are treated electrochemically between 0.0-1.2 V in potentiostatic (chronoamperometry) and potentiodynamic (cyclic voltametry) mode with reference to saturated calomel electrode. Reversible oxidation of Pt-0 to Pt2+ and Pt4+ state due to the applied positive potential is coupled to simultaneous reversible reduction of Ce4+ to Ce3+ state. CeO2 reduces to CeO2-y (y=0.35) after applying 1.2 V, which is not reversible; Ce0.98Pt0.02O2-delta reaches a steady state with Pt2+:Pt4+ in the ratio of 0.60:0.40 and Ce4+:Ce3+ in the ratio of 0.55:0.45 giving a composition Ce0.98Pt0.02O1.74 at 1.2 V, which is reversible. Composition of Pt ion substituted compound is reversible between Ce0.98Pt0.02O1.95 to Ce0.98Pt0.02O1.74 within the potential range of 0.0-1.2 V. Thus, Ce0.98Pt0.02O2-delta forms a stable electrode for oxidation of H2O to O-2 unlike CeO2. A linear relation between oxidation of Pt2+ to Pt4+ with simultaneous reduction in Ce4+ to Ce3+ is observed demonstrating Pt-CeO2 metal support interaction is due to reversible Pt-0/Pt2+/Pt4+ interaction with Ce4+/Ce3+ redox couple.

Asymptotic behaviour of point processes with Markov-dependent intervals

This splitting techniques for MARKOV chains developed by NUMMELIN (1978a) and ATHREYA and NEY (1978b) are used to derive an imbedded renewal process in WOLD's point process with MARKOV-correlated intervals. This leads to a simple proof of renewal theorems for such processes. In particular, a key renewal theorem is proved, from which analogues to both BLACKWELL's and BREIMAN's forms of the renewal theorem can be deduced.

Generation of H2O2 in biomembranes

Knowledge of the generation of H202 in cellular oxidations has existed for many years. It has been assumed that H202 is tOxiC tO cells and the presence of catalase is indicative of a detoxication mechanism. Other radicals of oxygen were recently recognized to be more potent destructive agents of biological material than H202. Also catalase and other peroxidases utilize H202 in some cellular oxidation processes leading to several important metabolites. Thus, the generation of H202 in cellular processes seems to be purposeful and H202 can not be dismissed as a mere undesirable byproduct. Biological formation of H202 is not limited to the previously known flavoproteins and some copper enzymes, but other redox systems, particularly heme and non-heme iron proteins, are now found to undergo auto-oxidation yielding H202. The capacity for generation of H202 is now found to be widespread in a variety of organisms and in the organdies of the cells. The reduction of oxygen to H20 by mitochondrial cytochrome oxidase being the predominant oxygen-utilizing reaction had over-shadowed the importance of the quantitatively minor pathways. Under aerobic conditions generation of H202 by a Variety of biomembranes has now been found to be a physiological event interlinked with phenomena such as phagocytosis, transport processes and thermogenesis in some as yet unidentified way. The underlying mechanisms of these processes seem to involve generation and utilization of H202 in mitochondria, microsomes, peroxisomes or plasma membranes. This review gives an account of the potential of biomembranes to generate H202 and its implication in the cellular processes.

Structural origin of set-reset processes in Ge15Te83Si2 glass investigated using in situ Raman scattering and transmission electron microscopy

We report here that the structural origin of an easily reversible Ge15Te83Si2 glass can be a promising candidate for phase change random access memories. In situ Raman scattering studies on Ge15Te83Si2 sample, undertaken during the amorphous set and reset processes, indicate that the degree of disorder in the glass is reduced from off to set state. It is also found that the local structure of the sample under reset condition is similar to that in the amorphous off state. Electron microscopic studies on switched samples indicate the formation of nanometric sized particles of c-SiTe2 structure. ©2009 American Institute of Physics

Adriamycin affects plasma membrane redox functions

Adriamycin (Doxorubicin) stimulates NADH oxidase activity in liver plasma membrane, but does not cause NADH oxidase activity to appear where it is not initially present, as in erythrocyte membrane. NADH dehydrogenase from rat liver and erythrocyte plasma membranes shows similar adriamycin effects with other electron acceptors. Both NADH ferricyanide reductase and vanadate-stimulated NADH oxidation are inhibited by adriamycin, as is a cyanide insensitive ascorbate oxidase activity, whereas NADH cytochrome c reductase is not affected. The effects may contribute to the growth inhibitory (control) and/or deleterious effects of adriamycin. It is clear that adriamycin effects on the plasma membrane dehydrogenase involve more than a simple catalysis of superoxide formation.