A highly efficient non-heme manganese complex in oxygenation reactions

A non-heme manganese(II) complex shows a high catalytic activity in the epoxidation of olefins by iodosyl benzene and in the oxidation of olefins, alcohols and alkanes by peracetic acid; a mechanism involving metal-based oxidants is proposed for the oxidation reactions.     

Cup-burner flame structure and extinguishment by CF3Br and C2HF5 in microgravity

The effects of fire-extinguishing agents CF₃Br and C₂HF₅ on the structure and extinguishing processes of microgravity cup-burner flames have been studied numerically. Propane and a propane–ethanol–water fuel mixture, prescribed for a Federal Aviation Administration (FAA) aerosol can explosion simulator test, were used as the fuel. The time-dependent, two-dimensional numerical code, which includes a detailed kinetic model (177 species and 2986 reactions), diffusive transport, and a gray-gas radiation model, revealed unique flame structure and predicted the minimum extinguishing concentration of agent when added to the air stream. The peak reactivity spot (i.e., reaction kernel) at the flame base stabilized a trailing flame. The calculated flame temperature along the trailing flame decreased downstream due to radiative cooling, causing local extinction at <1250 K and flame tip opening. As the mole fraction of agent in the coflow (X_a) was increased gradually: (1) the premixed-like reaction kernel weakened (i.e., lower heat release rate) (but nonetheless formed at higher temperature); (2) the flame base stabilized increasingly higher above the burner rim, parallel to the axis, until finally blowoff-type extinguishment occurred; (3) the calculated maximum flame temperature remained at nearly constant (≈1700 K) or mildly increased; and (4) the total heat release of the entire flame decreased (inhibited) for CF₃Br but increased (enhanced) for C₂HF₅. In the lifted flame base with added C₂HF₅, H₂O (formed from hydrocarbon-O₂ combustion) was converted further to HF and CF₂O through exothermic reactions, thus enhancing the heat-release rate peak. In the trailing flame, “two-zone” flame structure developed: CO₂ and CF₂O were formed primarily in the inner and outer zones, respectively, while HF was formed in both zones. As a result, the unusual (non-chain branching) reactions and the combustion enhancement (increased total heat release) due to the C₂HF₅ addition occurred primarily in the trailing diffusion flame.     

Natural radioactivity and radiation hazards assessment of soil samples from the area of Tuzla and Lukavac,Bosnia and Herzegovina

The results of activity concentration measurements of natural occurring radioactive nuclides ²³⁸U, ²³⁵U, ²³²Th, ²²⁶Ra, and ⁴⁰K in surface soil samples collected in the area of cities Tuzla and Lukavac, northeast region of Bosnia and Herzegovina were presented. Soil sampling was conducted at the localities that are situated in the vicinity of industrial zones of these cities. The measured activity was in the range from (8?±?4) to (95?±?28) Bq kg^–1 for ²³⁸U, from (0.41?±?0.06) to (4.6?±?0.7) Bq kg^–1 for ²³⁵U, from (7?±?1) to (66?±?7) Bq kg^–1 for ²³²Th, from (6?±?1) to (55?±?6) Bq kg^–1 for ²²⁶Ra, and from (83?±?12) to (546?±?55) Bq kg^–1 for ⁴⁰K. In order to evaluate the radiological hazard of the natural radioactivity for people living near industrial zones, the absorbed dose rate, the annual effective dose and the radium equivalent activity have been calculated and compared with the internationally approved values.     

Studies on electron transfer reactions: oxidation of phenol and ring-substituted phenols by heteropoly 11-tungstophosphovanadate(V) in aqueous acidic medium

The kinetics of oxidation of phenol and a few ring-substituted phenols by heteropoly 11-tungstophosphovanadate(V), [PV^VW₁₁O₄₀]⁴⁻ (HPA) have been studied spectrophotometrically in aqueous acidic medium containing perchloric acid and also in acetate buffers of several pH values at 25 °C. EPR and optical studies show that HPA is reduced to the one-electron reduced heteropoly blue (HPB) [PV^IVW₁₁O₄₀]⁵⁻. In acetate buffers, the build up and decay of the intermediate biphenoquinone show the generation of phenoxyl radical (ArO^·) in the rate-determining step. At constant pH, the reaction shows simple second-order kinetics with first-order dependence of rate on both [ArOH] and [HPA]. At constant [ArOH], the rate of the reaction increases with increase in pH. The plot of apparent second-order rate constant, k ₂, versus 1/[H⁺] is linear with finite intercept. This shows that both the undissociated phenol (ArOH) and the phenoxide ion (ArO⁻) are the reactive species. The ArO⁻–HPA reaction is the dominant pathway in acetate buffer and it proceeds through the OH⁻ ion triggered sequential proton transfer followed by electron transfer (PT-ET) mechanism. The rate constant for ArO⁻–HPA reaction, calculated using Marcus theory, agrees fairly well with the experimental value. The reactivity of substituted phenoxide ions correlates with the Hammett σ⁺ constants, and ρ value was found to be −4.8. In acidic medium, ArOH is the reactive species. Retardation of rate for the oxidation of C₆H₅OD in D₂O indicates breaking of the O–H bond in the rate-limiting step. The results of kinetic studies show that the HPA-ArOH reaction proceeds through a concerted proton-coupled electron transfer mechanism in which water acts as proton acceptor (separated-CPET).     

An acyclic,dansyl based colorimetric and fluorescent chemosensor for Hg(II) via twisted intramolecular charge transfer (TICT)

An efficient fluorescent chemosensor for Hg²⁺ ion, based on 5-(dimethylamino)-N-(2-mercaptophenyl)naphthalene-1-sulfonamide, has been developed. It exhibits Hg²⁺-selective on–off fluorescence quenching behavior via twisted intramolecular charge transfer (TICT) mechanism, which is rationalized by time dependent density functional theory (TD-DFT) calculations. The system exhibits visible color change from colorless to gray upon Hg²⁺ binding with very high selectivity and sensitivity (as low as 5.0 × 10⁻¹⁰ mol L⁻¹) over other metal ions such as K⁺, Na⁺, Ag⁺, Mn²⁺, Ca²⁺, Ba²⁺, Fe²⁺, Zn²⁺, Pb²⁺, Cu²⁺, Sn²⁺, Cd²⁺, Ni²⁺ and Co²⁺. The present sensing system is also successfully applied for the detection of Hg²⁺ ion in real samples.     

A novel Zn(4)O-based triazolyl benzoate MOF: synthesis, crystal structure, adsorption properties and solid state 13C NMR investigations

The newly synthesized Zn(4)O-based MOF (3)(∞)[Zn(4)(μ(4)-O){(Metrz-pba)(2)mPh}(3)]·8 DMF (1·8 DMF) of rare tungsten carbide (acs) topology exhibits a porosity of 43% and remarkably high thermal stability up to 430 °C. Single crystal X-ray structure analyses could be performed using as-synthesized as well as desolvated crystals. Besides the solvothermal synthesis of single crystals a scalable synthesis of microcrystalline material of the MOF is reported. Combined TG-MS and solid state NMR measurements reveal the presence of mobile DMF molecules in the pore system of the framework. Adsorption measurements confirm that the pore structure is fully accessible for nitrogen molecules at 77 K. The adsorptive pore volume of 0.41 cm(3) g(-1) correlates well with the pore volume of 0.43 cm(3) g(-1) estimated from the single crystal structure.     

On Growth Types of Quotients of Coxeter Groups by Parabolic Subgroups

The principal objects studied in this note are infinite, non-affine Coxeter groups W. A well-known result of de la Harpe asserts that such groups have exponential growth. We study the growth type of quotients of W by parabolic subgroups and by a certain class of reflection subgroups. Our main result is that these quotients have exponential growth as well.     

Hierarchically structured free-standing hydrogels with liquid crystalline domains and magnetic nanoparticles as dual physical cross-linkers

Here we report a modular strategy for preparing physically cross-linked and mechanically robust free-standing hydrogels comprising unique thermotropic liquid crystalline (LC) domains and magnetic nanoparticles both of which serve as the physical cross-linkers resulting in hydrogels that can be used as magnetically responsive soft actuators. A series of amphiphilic LC pentablock copolymers of poly(acrylic acid) (PAA), poly(5-cholesteryloxypentyl methacrylate) (PC5MA), and poly(ethylene oxide) (PEO) blocks in the sequence of PAA-PC5MA-PEO-PC5MA-PAA were prepared using reversible addition-fragmentation chain transfer polymerization. These pentablock copolymers served as macromolecular ligands to template Fe(3)O(4) magnetic nanoparticles (MNPs), which were directly anchored to the polymer chains through the coordination bonds with the carboxyl groups of PAA blocks. The resulting polymer/MNP nanocomposites comprised a complicated hierarchical structure in which polymer-coated MNP clusters were dispersed in a microsegregated pentablock copolymer matrix that further contained LC ordering. Upon swelling, the hierarchical structure was disrupted and converted to a network structure, in which MNP clusters were anchored to the polymer chains and LC domains stayed intact to connect solvated PEO and PAA blocks, leading to a free-standing LC magnetic hydrogel (LC ferrogel). By varying the PAA weight fraction (f(AA)) in the pentablock copolymers, the swelling degrees (Q) of the resulting LC ferrogels were tailored. Rheological experiments showed that these physically cross-linked free-standing LC ferrogels exhibit good mechanical strength with storage moduli G' of around 10(4)-10(5) Pa, similar to that of natural tissues. Furthermore, application of a magnetic field induced bending actuation of the LC ferrogels. Therefore, these physically cross-linked and mechanically robust LC ferrogels can be used as soft actuators and artificial muscles. Moreover, this design strategy is a versatile platform for incorporation of different types of nanoparticles (metallic, inorganic, biological, etc.) into multifunctional amphiphilic block copolymers, resulting in unique free-standing hybrid hydrogels of good mechanical strength and integrity with tailored properties and end applications.     

Photolytic-interference-free, femtosecond two-photon fluorescence imaging of atomic hydrogen

We discuss photolytic-interference-free, high-repetition-rate imaging of reaction intermediates in flames and plasmas using femtosecond (fs) multiphoton excitation. The high peak power of fs pulses enables efficient nonlinear excitation, while the low energy nearly eliminates interfering single-photon photodissociation processes. We demonstrate proof-of-principle, interference-free, two-photon laser-induced fluorescence line imaging of atomic hydrogen in hydrocarbon flames and discuss the method's implications for certain other atomic and molecular species.     

Multiple laminar-turbulent transition cycles around a swept leading edge

Certain interesting flow features involving multiple transition/relaminarization cycles on the leading edge of a swept wing at low speeds are reported here. The wing geometry tested had a circular nose and a leading edge sweep of 60°. Tests were made at a chord Reynolds number of 1.3 × 10⁶ with model incidence α varied in the range of 3°?18° in discrete steps. Measurements made included wing chord-wise surface pressure distributions and wall shear stress fluctuations (using hot-film gages) within about 10 % of the chord in the leading edge zone. Results at α = 16° and 18° showed that several (often incomplete) transition cycles between laminar-like and turbulent-like flows occurred. These rather surprising results are attributable chiefly to the fact that the Launder acceleration parameter K (appropriately modified for swept wings) can exceed a critical range more than once along the contour of the airfoil in the leading edge region. Each such crossing results in a relaminarization followed by direct retransition to turbulence as K drops to sufficiently low values. It is further shown that the extent of each observed transition zone (of either type) is consistent with earlier data acquired in more detailed studies of direct transition and relaminarization. Swept leading edge boundary layers therefore pose strong challenges to numerical modelling.