Solvent and deuterium isotope effects on the decomposition of ammonium nitrite solutions

The rate of decomposition of NH₄NO₂ solutions, at pH 5–7, equals k[NH₃] [HNO₂]² or k[NH ₄ ⁺ ] [NO ₂ ^– ][HNO₂]. A plausible mechanism involves a ratedetermining attack of N₂O₃, derived from HNO₂, on NH₃. H⁺⁺ and S⁺⁺ are 82 kJ-mol^–1 and –27 J-mol^–1-K^–1, respectively. On partially replacing the solvent water by methanol or ethanol, the change G⁺⁺, coupled with the calculated standard Gibbs energy of transfer of the reactants from water to the mixed solvent indicated that, in the latter, there is a greater destabilization of the transition state compared to that of the reactants. This can be explained by assuming two hydrogen bonds from the same water molecule to the transition state and hence a loss of hydrogen bond energy in the mixed solvent compared to the aqueous solution. The rate constant for the reaction of ND₄NO₂ in D₂O compared to the reaction of NH₄NO₂ in water, gave a composite isotope effect involving two acid-base equilibria, suggested in the proposed mechanism; in addition to primary isotope effects in the equilibrium: 2 HNO₂N₂O₃+H₂O.     

Enzymatic synthesis of alkyl arabinofuranosides using a thermostable α-l-arabinofuranosidase

A thermostable α-l-arabinofuranosidase was tested for its ability to perform transglycosylation with different alcohol acceptors. Reactions were characterized by high rates with optimal synthesis being obtained within 10 min. Both primary and secondary alcohols could act as acceptors in transarabinosylation but yields of alkyl arabinosides decreased with increasing alkyl chain length.     

Distribution of heavy metal concentrations in surface sediments in Dubai Creeks, United Arab Emirates

Dubai is developing rapidly and many developmental activities are concentrated around its Creek. The present study reports the lateral distribution of heavy metals and compares it with local historical record of heavy metal concentrations. For this purpose surface sediment samples were collected and analyzed for metal contents, total organic carbon content (TOC), mineralogy and grain size. The percentages of the different grain size fraction of the collected sediments were as follow 65% for sand size, 15% for silt size fraction, and the rest accounted for clay size fraction. The microscopic analyses indicate that the sediment composed mainly from carbonate and quartz with traces of rock fragments. Such mineral composition is not believed to be a potential source of heavy metal. The study found that the average recorded heavy metal concentrations in the collected sediment samples were 87, 96, 127, 38.5, and 279 ppm for Cr, Cu, Ni, Pb, and Zn, respectively. Those values were slightly higher than metal concentrations recoded in 2001 with 1.22 (Cr), 2.5 (Cu), 2.87 (Ni), 0.69 (Pb), and 2.1 (Zn) folds. However, in 2001 and 2003 the measured metal contents, along the creek, were lower than those of the average earth crust. Along the Creek most metals recorded the highest concentrations in the upper reach of the Creek. The distribution of the measured heavy metals was not affected significantly with the TOC values. The present study also documented obvious related point sources of pollution.     

Lateral and vertical nanophase separation in Langmuir-Blodgett films of phospholipids and semifluorinated alkanes

It has recently been found that monodisperse surface micelles (hemimicelles) were formed in Langmuir monolayers of the semifluorinated alkane C8F17C16H33 (F8H16) after transfer onto silicon wafers. Grazing incidence X-ray diffraction studies have demonstrated that compression of mixed Langmuir monolayers made from combinations of dipalmitoyl phosphatidylethanolamine (DPPE) and diblock F8H16 in various molar ratios resulted in the complete expulsion of the diblock molecule at high surface pressure. F8H16 then formed a second layer on top of a DPPE-only monolayer, demonstrating a novel type of reversible, pressure-induced, vertical phase separation. Using atomic force microscopy and X-ray reflectivity, we show now that mixed DPPE/F8H16 (1:1.3) Langmuir-Blodgett films transferred onto silicon wafers below 10 mN m(-1) are laterally phase separated and consist of domains of F8H16 surface micelles in coexistence with a monolayer of DPPE. The density of the network of F8H16 surface micelles increases when the surface pressure of transfer increases. Around 10 mN m(-1), the F8H16 surface micelles start to glide on the DPPE monolayer, progressively overlying it, until total coverage is achieved.     

Synthesis and properties of 7-formyl-8-hydroxyquinoline and its transition metal complexes

Summary Co^II, Ni^II, Cu^II, Cd^II and Hg^II complexes of 7-formyl-8-hydroxyquinoline (HFHQ) have been prepared, and characterized by elemental analysis, molar conductivities, electronic and i.r. spectra, and magnetic measurements. It was found that the ligand acts as a neutral monodentate or a monobasic bidentate donor. The Co^II, Ni^II and Cu^II complexes possess, respectively, tetrahedral, octahedral and square-planar structures based on their magnetic and electronic spectral data. The electrical conductivities of HFHQ and its metal complexes were measured at different temperatures and their activation energies were calculated. The values obtained for the Co^II, Ni^II, Cd^II and Hg^II complexes agree fairly well with those reported for semiconductors. The ligand was tested as a corrosion inhibitor for aluminium; the limiting concentration of HFHQ to give maximum efficiency (99.2%) is 10^–3 mole dm^–3 at 22°C. The metal-ligand ratios and apparent formation constants for the species generated in ethanol solution were determined spectrophotometrically.     

Decay rates of the solution of the Cauchy thermoelastic Bresse system

We consider two Cauchy problems for the one-dimensional thermoelastic Bresse model. Using the energy method in the Fourier space, we show that for the first model, the \({L^{2}}\)-norm of the solution decays with the rate \({(1+t)^{-1/12}}\). In addition, the same decay rate has been obtained for the second model.     

Hierarchical Self‐Assembly of Supramolecular Muscle‐Like Fibers

An acid–base switchable [c2]daisy chain rotaxane terminated with two 2,6‐diacetylamino pyridine units has been self‐assembled with a bis(uracil) linker. The complementary hydrogen‐bond recognition patterns, together with lateral van der Waals aggregations, result in the hierarchical formation of unidimensional supramolecular polymers associated in bundles of muscle‐like fibers. Microscopic and scattering techniques reveal that the mesoscopic structure of these bundles depends on the extended or contracted states that the rotaxanes show within individual polymer chains. The observed local dynamics span over several length scales because of a combination of supramolecular and mechanical bonds. This work illustrates the possibility to modify the hierarchical mesoscopic structuring of large polymeric systems by the integrated actuation of individual molecular machines.     

Thermal diffusion and molecular diffusion values for some alkane mixtures: a comparison between thermogravitational column and thermal diffusion forced rayleigh scattering

In the present work we studied the thermal diffusion behavior of n-decane in various alkanes by thermogravitational column (TC) technique and the thermal diffusion forced Rayleigh scattering (TDFRS) method. The investigated lighter alkanes compared to n-decane are n-pentane, n-hexane, n-heptane, n-octane, and the heavier ones are n-tetradecane, n-pentadecane, n-hexadecane, n-heptadecane, n-octadecane, and n-eicosane. The binary mixture n-decane/ n-pentane we investigated at several different concentrations; all other mixtures were only investigated at a mass fraction of 50%. Even for the volatile n-pentane/ n-decane mixture the deviations between the thermal diffusion coefficients determined by the different methods agreed within the error bars. Typically the agreement between the two methods was in the order of 5%. In comparison to recently published TC and TDFRS data we found deviations in the order of 30% up to 40%. We analyze and discuss the possible reasons for the discrepancies for the present and the past publications.     

Gating motions in voltage-gated potassium channels revealed by coarse-grained molecular dynamics simulations

Voltage-gated potassium (Kv) channels are ubiquitous transmembrane proteins involved in electric signaling of excitable tissues. A fundamental property of these channels is the ability to open or close in response to changes in the membrane potential. To date, their structure-based activation mechanism remains unclear, and there is a large controversy on how these gates function at the molecular level, in particular, how movements of the voltage sensor domain are coupled to channel gating. So far, all mechanisms proposed for this coupling are based on the crystal structure of the open voltage-gated Kv1.2 channel and structural models of the closed form based on electrophysiology experiments. Here, we use coarse-grain (CG) molecular dynamics simulations that allow conformational changes from the open to the closed form of the channel (embedded in its membrane environment) to be followed. Despite the low specificity of the CG force field, the obtained closed structure satisfies several experimental constraints. The overall results suggest a gating mechanism in which a lateral displacement the S4-S5 linker leads to a closing of the gate. Only a small up-down movement of the S4 helices is noticed. Additionally, the study suggests a peculiar upward motion of the intracellular tetramerization domain of the channel, hence providing a molecular view on how this domain may further regulate conduction in Kv channels.