The Redox Chemistry of Manganese(III) and -(IV) Complexes

The oxidation-reduction thermodynamics for the manganese(III), -(IV), and -(II) ions, and their various complexes, are reviewed for both aqueous and aprotic media. In aqueous solutions the reduction potential for the manganese(III)/(II) couple has values that range from +1.51 V vs. NHE (hydrate at pH 0) to −0.95 V (glucarate complex at pH 13.5). The Mn(IV)/(III) couple has values that range from +1.0 V (solid Mn^IVO₃ at pH 0) to −0.04 V (tris gluconate complex at pH 13.5). With anhydrous media the propensity for the Mn(III) ion to disproportionate to solid Mn^IVO₂ and Mn(II) ion is avoided. For aprotic systems the range of redox potentials for various manganese complexes is from +2.01 V and +1.30 for the Mn(IV)/(III) and Mn(III)/(II) couples (bis terpyridyl tri-N-oxide complex in MeCN), respectively, to −0.96 V for the Mn(IV)/(III) couple (tris 3,5,-di-tert-butylcatecholate complex in Me₂SO). The redox reactions between manganese complexes and dioxygen species (O₂, O₂, and H₂O₂) also are reviewed.     

The effect of salinity on nitrite accumulation in a down‐flow hanging sponge reactor

BACKGROUND: In this study, the inductive effect of salinity on nitrite accumulation in a down‐flow hanging sponge (DHS) reactor, developed as a novel and cost‐effective wastewater treatment process, was evaluated by conducting a long‐term continuous experiment lasting more than 1400 days. RESULTS: The influent salinity was controlled by adding NaCl at concentrations ranging from 0 to 25 g Cl^? L^?1. The effluent nitrite increased with increases in salinity, i.e. the fraction of nitrite to total nitrogen in the effluent increased from 1.6% at 0 g Cl^? L^?1 to 87.6% at 25 g Cl^? L^?1. Fluorescence in situ hybridization (FISH) analysis revealed that as salinity increased, the nitrifying bacterial community in the DHS changed markedly at the species level. In particular, the dominant nitrite‐oxidizing bacteria changed from Nitrospira‐sublineage I at 0 g Cl^? L^?1 to Nitrobacter spp. at 15 g Cl^? L^?1. At 25 g Cl^? L^?1, no nitrite‐oxidizing bacteria were detected. CONCLUSION: Our findings suggest that the DHS reactor is suitable for cost‐effective nitrite production processes and that salinity control using NaCl is an effective method for inducing nitrite accumulation. Copyright © 2012 Society of Chemical Industry     

Fabrication of submicron alumina ceramics by pulse electric current sintering using M2+ (M = Mg,Ca, Ni)-doped alumina nanopowders

Dense submicron-grained alumina ceramics were fabricated by pulse electric current sintering (PECS) using M²⁺(M: Mg, Ca, Ni)-doped alumina nanopowders at 1250 °C under a uniaxial pressure of 80 MPa. The M²⁺-doped alumina nanopowders (0–0.10 mass%) were prepared through a new sol–gel route using high-purity polyhydroxoaluminum (PHA) and MCl₂ solutions as starting materials. The composite gels obtained were calcined at 900 °C and ground by planetary ball milling. The powders were re-calcined at 900 °C to increase the content of α-alumina particles, which act as seeding for low-temperature densification. Densification and microstructural development depend on the M²⁺ dopant species. Dense alumina ceramics (relative density ≥99.0%) thus obtained had a uniform microstructure composed of fine grains, where the average grain size developed for non-doped, Ni-doped, Mg-doped and Ca-doped samples was 0.67, 0.67, 0.47 and 0.30 μm, respectively, showing that Ca-doping is the most promising method for tailoring of nanocrystalline alumina ceramics.     

Phospholipid polymer hydrogel formed by the photodimerization of cinnamoyl groups in the polymer side chain

We synthesized new polymers with both photocrosslinkability and biocompatibility by a random copolymerization of 4‐(4‐methoxycinnamoyl)phenyl methacrylate and 2‐methacryloyloxyethyl phosphorylcholine. These polymers were used as prepolymers to make a hydrogel by photoirradiation. Gelation began with 5 s of photoirradiation and reached an equilibrium state after 360 s of photoirradiation. The absorption maximum at 347 nm, attributed to the cinnamoyl group, disappeared with the photoirradiation time. That is, dimerization between cinnamoyl groups in the polymer proceeded and formed a hydrogel. The equilibrium water concentration of the hydrogels was more than 90%. Moreover, we succeeded in making a microshape hydrogel on glass by photoirradiation through a photomask. The window shape of the photomask was transferred to the hydrogel that was formed. We concluded that these photocrosslinkable polymers could be useful in preparing microfluidic devices for separating or immobilizing biomolecules and cells. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 44–50, 2007     

Preparation of novel porous solids from alumina-pillared fluorine micas by acid-treatment

New porous solids from alumina-pillared fluorine micas (APMs), which were obtained from synthetic Na-tetrasilicic fluorine mica [NaMg_2.5Si₄O₁₀F₂], were prepared by sulfuric acid-treatment under mild conditions at 25 °C. The products were investigated by XRD, ICP, SEM, TEM and N₂ adsorption–desorption isotherm at 77 K. XRD measurements indicated that the interlayer pillared structure having a large basal spacing collapsed during the early stages of the acid-treatment. ICP analyses indicated that Al³⁺ and Mg²⁺ ions were leached out from the pillared micas during the acid-treatment. The pore properties of the leached products were found to differ from those of the mother pillared micas: the acid leaching of the pillared micas leads to the formation of mesopores around 3.2 nm in diameter. The correlation between the change in pore properties and cation elution behavior suggests that the mesopore formation results from the leaching of Mg²⁺ ions from the octahedral sheet of the pillared micas. The leached products thus obtained retained the flaky morphology of the mother pillared micas. These results show that the mild acid-treatment using APMs provides a novel route for obtaining unique mesopore solids having the large particle sizes of the mother micas.     

Optical polarisation control utilising an optical heterodyne detection scheme

An optical polarisation control scheme utilising optical heterodyne detection for coherent transmission is proposed and demonstrated at a wavelength of 1.5 ?m. It converts an arbitrary polarisation state to a linear state at a received optical power level of less than ?70 dBm.     

A 64 kbit/s Integrated Visual Communication System--New Communication Medium for the ISDN

Seeing-while-talking has been a dream of mankind for over a 100 years since the invention of telephone. In the past, various trials were performed in spite of the difficulty in installing the network for the actual service. However, with the progress of ISDN and the advancement of digital signal processing technology, the environment has been changing rapidly. In this paper, an integrated visual communication system is described for the enhanced communication service at 64 kbits/s, the fundamental bit rate of ISDN. The roles of state-of-theart compression of the audio and video signals are discussed and an integrated transmission method based on the priority of the information content is proposed.     

Facilitation of acetylcholine release in rat frontal cortex by indeloxazine hydrochloride: involvement of endogenous serotonin and 5-HT4 receptors

Effects of indeloxazine hydrochloride, an inhibitor of serotonin (5-HT) and norepinephrine (NE) reuptake with a facilitatory effect on 5-HT release, on acetylcholine (ACh) output in frontal cortex of conscious rats were characterized using an in vivo microdialysis technique. Systemic administration of indeloxazine (3 and 10 mg/kg, i.p.) increased ACh and 5-HT output in a dose-dependent manner. Depletion of endogenous monoamines by reserpine and of 5-HT by p-chlorophenylalanine, but not that of catecholamines by alpha-methyl-p-tyrosine, significantly attenuated the facilitatory effect of indeloxazine on ACh release. When applied locally by reverse dialysis, indeloxazine (10 and 30 microM) and the selective 5-HT reuptake inhibitor citalopram (10 microM), but not the NE reuptake inhibitor maprotiline (30 microM), increased cortical ACh output. Indeloxazine (10 mg/kg)-induced increase in ACh release was significantly inhibited by local application of the 5-HT4 receptor antagonists RS23597 (50 microM) and GR113803 (1 microM), while the 5-HT1A antagonist WAY-100135 (100 microM), 5-HT1A/1B/beta-adrenoceptor antagonist (-)propranolol (150 microM), 5-HT2A/2C antagonist ritanserin (10 microM) and 5-HT3 antagonist ondansetron (10 microM) failed to significantly modify this effect. Neither depletion of monoamines nor treatment with serotonergic antagonists significantly changed the basal ACh level, indicating that endogenous monoamines do not tonically activate ACh release. These results suggest that indeloxazine-induced facilitation of ACh release in rat frontal cortex is mediated by endogenous 5-HT and involves at least in part cortical 5-HT4 receptors.