Electrochemical reduction of nitrate on Pt(S)[n(1 1 1) × (1 1 1)] electrodes in perchloric acid solution

The electrochemical reduction of nitrate ion was studied by cyclic voltammetry on Pt(1 1 1) and [n(1 1 1) × (1 1 1)] stepped Pt surfaces, where n (=14, 10, 7, 6, 5, 4, 3, 2) is the number of terrace atoms, in 0.1 M HClO₄ + 10 mM KNO₃. The electrocatalytic nitrate reduction was found to hardly proceed on Pt(1 1 1) in the hydrogen adsorption region, while the electrocatalytic activity was improved with the increase in the step density. Inactivation was observed in the presence of adsorbed hydrogen or nitrate-derived reduced adsorbate, i.e. adsorbed NO, on (1 1 1) step sites. It was, therefore, concluded that the electrocatalytically active NO₃⁻ species does not adsorb on the (1 1 1) terraces but on the (1 1 1) monoatomic steps. The nitrate reduction current increased with the step density in a non-linear relationship. The overall current density at 0.21 V (RHE) corresponding to the peak potential of the main electrocatalytic nitrate reduction wave which was maximum at n = 2, abruptly increased with short terraces, i.e. n < 5, where the current wave of adsorbed hydrogen on the Pt stepped surface with comparatively narrow (1 1 1) terraces, denoted as H_nt, also appeared unmodified for n < 5 on voltammograms recorded in 0.1 M HClO₄ in the absence of nitrate.     

Fabrication of Nonadditive Mica Ceramics by Hot Isostatic Processing

Powder compacts of synthetic mica (fluorphlogopite) encapsulated in a boro–silicate glass tube were isostatically hot–pressed in a Roy–Tuttle–type pressure vessel. Synthetic mica was sintered to a density of 2.60 g/cm³ (91.2% of theoretical density) without additives under 98 MPa of water at 800°C for 45 min.     

A PRACTICAL METHOD FOR RECTIFYING INTERFACIAL TENSION DATA TO PREDICT THE SHAPE OF INTERFACES IN AN IMMISCIBLE LIQUID/LIQUID/GAS SYSTEM

The shape of interfaces formed by the contact of two liquid phases, immiscible with each other, and a gaseous phase can be predicted on the condition that the tension to work at each interface is known with a sufficient accuracy. In general, interfacial tension data available are not so accurate, however, as to be useful as they are in predicting the shape of interfaces, particularly when the spreading coefficient of either liquid (liquid 1) on the other (liquid 2) has a negative value of a small magnitude. Presented in this note is a simple method to rectify the interfacial tension data, with the aid of a measurement of the radius of a lens of liquid 1 of a known volume placed on the horizontal surface of liquid 2, and thereby make them usable for predicting interfacial geometries. The method is tested by applying it to benzene/water and n-pentane/water systems.     

Role of tungsten in promoting selective reduction of NO with CO over Ir/WO3–SiO2 catalysts

Catalytic hydrogenation of naphthalene to decalin was studied over a carbon-supported rhodium catalyst in supercritical carbon dioxide solvent at 333 K, and the results were compared with those in an organic solvent. cis-, trans-Decalin and tetralin were formed from the beginning of the reaction in supercritical carbon dioxide. Higher concentration of hydrogen in carbon dioxide solvent and on the active site, and also the suppression of desorption of partially hydrogenated tetralin molecules from the active site would be responsible for higher selectivity to cis-decalin in supercritical carbon dioxide than that in an organic solvent.     

Synthesis of well-defined poly(styrene)-b-poly(p-tert-butoxystyrene) multiblock copolymer from poly(alkoxyamine) macroinitiator

The stepwise insertion reaction of styrene (St) and p-tert-butoxystyrene (BOSt) into poly(alkoxyamine) macroinitiator was carried out to provide well-defined poly(St)-b-poly(BOSt) multiblock copolymers. Structural confirmation of the multiblock copolymers was accomplished by NMR and IR measurements. The model reaction also supported that the monomer insertion into the macroinitiator proceeded in accordance with a living fashion.     

An absolute requirement of fructose 1,6-bisphosphate for the Lactobacillus caseiL-lactate dehydrogenase activity induced by a single amino acid substitution

Lactobacillus casei allosteric L-lactate dehydrogenase (L-LDH)absolutely requires fructose 1,6-bisphosphate [Fru(1,6)P2] forits catalytic activity under neutral conditions, but exhibitsmarked catalytic activity in the absence of Fru(1,6)P₂ underacidic conditions through the homotropic activation effect ofsubstrate pyruvate. In this enzyme, a single amino acid replacement,i.e. that of His205 conserved in the Fru(1,6)P₂-binding siteof certain allosteric L-LDHs of lactic acid bacteria with Thr,did not induce a marked loss of the activation effect of Fru(1,6)P₂or divalent metal ions, which are potent activators that improvethe activation function of Fru(1,6)P₂ under neutral conditions.However, this replacement induced a great loss of the Fru(1,6)P₂-independentactivation effect of pyruvate or pyruvate analogs under acidicconditions, consequently indicating an absolute Fru(1,6)P₂ requirementfor the enzyme activity. The replacement also induced a significantreduction in the pH-dependent sensitivity of the enzyme to Fru(1,6)P₂,through a slight decrease and increase of the Fru(1,6)P₂ sensitivityunder acidic and neutral conditions, respectively, indicatingthat His205 is also largely involved in the pH-dependent sensitivityof L.casei L-LDH to Fru(1,6)P₂. The role of His205 in the allostericregulation of the enzyme is discussed on the basis of the knowncrystal structures of L-LDHs.     

Allelopathic Effects of Volatile Monoterpenoids Produced by <Emphasis Type="Italic">Salvia leucophylla</Emphasis>: Inhibition of Cell Proliferation and DNA Synthesis in the Root Apical Meristem of <Emphasis Type="Italic">Brassica campestris</Emphasis> Seedlings

Salvia leucophylla, a shrub observed in coastal south California, produces several volatile monoterpenoids (camphor, 1,8-cineole, -pinene, -pinene, and camphene) that potentially act as allelochemicals. The effects of these were examined using Brassica campestris as the test plant. Camphor, 1,8-cineole, and -pinene inhibited germination of B. campestris seeds at high concentrations, whereas -pinene and camphene did not. Root growth was inhibited by all five monoterpenoids in a dose-dependent manner, but hypocotyl growth was largely unaffected. The monoterpenoids did not alter the sizes of matured cells in either hypocotyls or roots, indicating that cell expansion is relatively insensitive to these compounds. They did not decrease the mitotic index in the shoot apical region, but specifically lowered mitotic index in the root apical meristem. Moreover, morphological and biochemical analyses on the incorporation of 5-bromo-2-deoxyuridine into DNA demonstrated that the monoterpenoids inhibit both cell-nuclear and organelle DNA synthesis in the root apical meristem. These results suggest that the monoterpenoids produced by S. leucophylla could interfere with the growth of other plants in its vicinity through inhibition of cell proliferation in the root apical meristem.     

Sulfur exchange on Co---Mo/Al2O3 hydrodesulfurization catalyst using S radioisotope tracer

A commercial Co---Mo/Al₂O₃ catalyst was labeled with the radioisotope ³⁵S in hydrodesulfurization (HDS) of ³⁵S-labeled dibenzothiophene (³⁵S-DBT) in a high-pressure flow reactor at 50 kg/cm². Then, HDS of 4-methyldibenzothiophene (4-MDBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) or sulfur exchange of H₂S were carried out on the labeled catalyst at 50 kg/cm² and 260–360°C. The amounts of labile sulfur participating in the reaction were determined from the radioactivity of ³⁵S---H₂S released from the ³⁵S-labeled catalyst. In the HDS reactions, the amount of labile sulfur participating in the reaction decreased in the order: DBT> 4-MDBT> 4,6-DMDBT. In the sulfur exchange reaction with H₂S, the adsorption of H₂S on the catalyst reached saturation above a H₂S partial pressure of 0.36 kg/cm². It was suggested that the release of H₂S from the labile sulfur may be the rate determining step of the HDS reaction.     

Effect of zeolite in surface discharge plasma on the decomposition of toluene

Toluene was decomposed in a surface discharge plasma reactor packed with various zeolites. The positioning effect of the zeolite bed was also investigated Reactor-B, in which the zeolite bed was located upstream, performed much better than Reactor-A, in which the zeolite bed was located downstream. Furthermore, the decomposition efficiency in Reactor-B increased with the capacity for toluene adsorption on zeolite, while that in Reactor-A did not. The toluene adsorbed in micropores was not decomposed effectively by direct electron impact, but was decomposed by active oxygen species generated in the plasma zone on the zeolite surface. A good correlation was also observed between toluene decomposition and ozone consumption in the downward-type reactor.     

Application of polymerizable surfactant in the preparation of polystyrene/nano-Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> composite

Monooctadecyl maleate, as a polymerizable surfactant, was synthesized by the mono-esterification of maleic anhydride and octadecanol, and was utilized to surface-modify nano-Fe₃O₄ particles. A polymerizable magnetic fluid was obtained by directly dispersing modified nano-Fe₃O₄ particles into styrene monomer, and the polystyrene/nano-Fe₃O₄ composite was prepared through free radical polymerization of polymerizable magnetic fluid. The structure and dispersion status in different dispersion phases of modified nano-Fe₃O₄ particles were studied by Fourier transform infrared (FTIR) spectrometry, X-ray diffraction (XRD) and transmission electron microscopy (TEM), respectively. The experimental results show that the nano-Fe₃O₄ particles modified by monooctadecyl maleate with the size of about 7–10 nm can be uniformly dispersed into styrene and fixed in the composite during the procedure of polymerization. Thermogravimetric analysis (TGA) and vibrating sample magnetometry (VSM) indicate that the thermal stability of polystyrene/nano-Fe₃O₄ composite is improved compared to that of pure polystyrene, and the composite is a sort of superparamagnetic materials.