Synthesis of N,N-diethyl-N-{4-[(E)-(4-nitrophenyl)diazenyl]phenyl}amine via in situ diazotisation and coupling in supercritical carbon dioxide

The synthesis of azo dyes via a conventional aqueous-based diazotisation and coupling reaction requires the use of relatively high concentrations of mineral acids, which leads to high electrolyte concentrations in wastewater. Reported in this paper is an environmentally benign one-pot method for the synthesis of a nonionic azo dye, N,N -diethyl- N -{4-[( E )-(4-nitrophenyl)diazenyl]phenyl}amine, in supercritical carbon dioxide without using a mineral acid. The product yield increased significantly with temperature, with 91% theoretical yield afforded at 80 °C. The pressure of the system had little influence on product yield.     

Selective oxidation of alcohols using octahedral molecular sieves: influence of synthesis method and property–activity relations

Manganese oxides having a tunnel structure (OMS-2) have been utilized as selective catalysts for alcohol oxidation. In this study manganese oxide catalysts were synthesized in different media and modified by exchanging the tunnel cation by H⁺, using acid treatment or exchanging with NH₄⁺ followed by thermolysis. Various alcohol oxidations were performed using these catalysts to ascertain the influence of synthesis method on their activity. A correlation is made between lattice oxygen instability and activity of the catalysts, which indicates involvement of the lattice oxygen in the mechanism. The exchange of the tunnel cation with the smaller H⁺ ions leads to weakening of the Mn–O bond, as verified by temperature programmed desorption (TPD) results. Only the chemisorbed oxygen on the surface (O⁻) and the lattice oxygen in the layers close to the surface is involved in the oxygen transfer during the reaction.     

Enzyme‐catalyzed hydrolysis of poly(ethylene terephthalate) cyclic trimer

Oligoesters present in poly(ethylene terephthalate) fibers are commonly extracted from the fiber during processing, such as aqueous‐based dyeing. Aqueous, insoluble oligoesters, particularly cyclic trimers that precipitate on processing machinery and on the fiber surface are difficult to remove under benign conditions. Reported is a new method for the efficient removal of cyclic trimer by enzyme‐catalyzed hydrolysis. Almost complete hydrolysis of trimer was accomplished at pH 8 and 60°C. Effects of time, agitation, surfactant, and enzyme and trimer concentrations on the efficiency of hydrolysis are reported. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2545–2552, 2003     

A comparison of vapour pressure measurements of quinizarin and leuco-quinizarin via transpiration and thermogravimetry

The vapour pressure of solids can be obtained using a number of methods, including the Knudsen effusion method, the Knudsen torque-effusion method and a transpiration method. Each method has benefits and disadvantages. Reported is a comparison of vapour pressure data for two compounds, quinizarin and leuco -quinizarin, using a transpiration method and a recently developed method based on thermogravimetry. Thermogravimetry provided vapour pressure–temperature dependence data for each compound with expediency and in agreement with the transpiration method.     

Formation of Gold Clusters on TiO2 from Adsorbed Au(CH3)2(C5H7O2): Characterization by X-ray Absorption Spectroscopy

Gold nanoclusters on TiO₂ powder were prepared from adsorbed Au^III(CH₃)₂(C₅H₇O₂) (dimethyl acetylacetonate gold(III)) and characterized by extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES) spectroscopies. The samples were tested as catalysts for CO oxidation at 298 K and atmospheric pressure and characterized by EXAFS and XANES with the catalysts in the working state. The XANES results identify Au(III) in the initially prepared sample, and the EXAFS data indicate mononuclear gold complexes as the predominant surface gold species in this sample, consistent with the lack of Au–Au contributions in the EXAFS spectrum. The mononuclear gold complex is bonded to two oxygen atoms of the TiO₂ surface at an Au–O distance of 2.16 Å. Treatment of this complex in He or in H₂ at increasing temperatures led to formation of metallic gold clusters of increasing size, ultimately those with an average diameter of about 15 Å. The data demonstrate the presence of metallic gold clusters in the working catalysts and also show these clusters alone are not responsible for the catalytic activity.     

Incidence of an Ozonation Stage on the Treatment of Cherry Stillage by Activated Sludge

This article presents a laboratory study of the ozonation of diluted cherry stillage, a high-strength wastewater. Influence of variables, kinetics, and the effects of an ozonation stage coupled with the biological treatment by activated sludge are addressed. Single activated sludge processing was shown effective to remove biological oxygen demand (BOD) and chemical oxygen demand (COD) but polyphenols were reduced to a lesser extent. On the other hand, direct wastewater ozonation did not reduce COD and total organic carbon (TOC) appreciably, and foaming problems were experienced when a high gas flow rate was applied. However, polyphenols and UV₂₅₄ absorbance decreased substantially by means of ozonation. To best achieve complete cherry stillage purification, two ways of coupling ozonation with activated sludge are proposed. Ozonation prior to activated sludge is advised for high-concentration wastewater to reduce polyphenol concentration, thus removing inhibiting effects. For wastewater with low polyphenol concentration the sequence activated sludge–ozonation–activated sludge is preferred to enhance the overall process performance in terms of oxidation efficiency and sludge settling.     

Carbon monoxide oxidation and nitrous oxide reduction on Rh/Pt(1 1 1) electrodes

Rhodium adlayers on Pt(1 1 1) substrates have been prepared by electrodeposition from dilute Rh³⁺ acidic solutions. Resulting deposition rates are lower than 0.03 ML min⁻¹. Pseudomorphic growth of the first monolayer has been confirmed by scanning tunneling microscopy (STM) as well as the formation of small compact islands in the submonolayer range. Carbon monoxide oxidation and nitrous oxide reduction have been studied on Rh/Pt(1 1 1) electrodes. The oxidation of carbon monoxide is catalyzed by the presence of very low coverages of rhodium as demonstrated by the negative shift of the CO oxidation profile. Results are compatible with a bifunctional mechanism for catalysis including CO diffusion in the Pt domains toward the edges of the islands (splitting of the voltammetric oxidation profile). The reduction of nitrous oxide occurs at different potential and with different rates on Pt domains, at the center of the Rh islands and at their edges, being the latter sites especially active. In any case, the adsorptive and catalytic activity of the adlayers differ from those of the bulk Pt(1 1 1) and Rh(1 1 1) electrodes. The existence of strain in the film together with a diminution in the coordination number for adatoms at the edges of the islands are considered to be at the origin of the observed behavior.     

Accelerated Aging in 3-mol%-Yttria-Stabilized Tetragonal Zirconia Ceramics Sintered in Reducing Conditions

The aging behavior of 3-mol%-yttria-stabilized tetragonal zirconia (3Y-TZP) ceramics sintered in air and in reducing conditions was investigated at 140°C in water vapor. It was observed by X-ray diffraction (XRD) that 3Y-TZP samples sintered in reducing conditions exhibited significantly higher tetragonal-to-monoclinic transformation than samples with similar density and average grain size values but obtained by sintering in air. This fact is explained by the increase of the oxygen vacancy concentration and by the presence at the grain boundary region of a new aggregate phase formed because of the exolution of Fe²⁺ ions observed by X-ray photoelectron spectroscopy.     

NMR and modeling studies of protein-carbohydrate interactions: synthesis, three-dimensional structure, and recognition properties of a minimum hevein domain with binding affinity for chitooligosaccharides

HEV32, a 32-residue, truncated hevein lacking eleven C-terminal amino acids, was synthesized by solid-phase methodology and correctly folded with three cysteine bridge pairs. The affinities of HEV32 for small chitin fragments--in the forms of N,N',N"-triacetylchitotriose ((GlcNAc)3) (millimolar) and N,N',N",N"',N",N"'-hexaacetylchitohexaose ((GlcNAc)6) (micromolar)--as measured by NMR and fluorescence methods, are comparable with those of native hevein. The HEV32 ligand-binding process is enthalpy driven, while entropy opposes binding. The NMR structure of ligand-bound HEV32 in aqueous solution was determined to be highly similar to the NMR structure of ligand-bound hevein. Solvated molecular-dynamics simulations were performed in order to monitor the changes in side-chain conformation of the binding site of HEV32 and hevein upon interaction with ligands. The calculations suggest that the Trp21 side-chain orientation of HEV32 in the free form differs from that in the bound state; this agrees with fluorescence and thermodynamic data. HEV32 provides a simple molecular model for studying protein-carbohydrate interactions and for understanding the physiological relevance of small native hevein domains lacking C-terminal residues.