Cation Transport at 25°C from Binary Cd2+–Mn+ Mixtures in a H2O-CHCl3–H2O Liquid Membrane System Containing a Series of Macrocyclic Carriers[1]

Macrocycle-mediated fluxes of Cd(NO₃)₂ and of several binary mixtures of Cd(NO₃)₂ with the nitrate salt of either Na⁺, K⁺, Rb⁺ Cs⁺, Ag⁺, Ca²⁺, Sr²⁺, Pb²⁺, Zn²⁺, or Cu²⁺ have been determined in a H₂O-CHCl₃–H₂O liquid membrane system. Of the macrocycles studied, 2.2 and 2.2DD most successfully transported Cd²⁺ In the Cd²⁺–Mⁿ⁺ mixtures, Cd²⁺ was transported selectively with 2.2 when Mⁿ⁺ was either an alkali or an alkaline earth cation. However, when Mⁿ⁺ was either Ag⁺, Pb²⁺, or Cu²⁺ the Cd²⁺ flux was reduced sharply. Generally, cation flux was greater for 2.2DD than for 2.2 with selectivity for Cd²⁺ being altered also in several cases. Relative fluxes from binary cation mixtures depend on metal cation radius, macrocycle cavity diameter, ligand ring substituent and log K for metal ion-macrocycle interaction.     

A New Indole Synthesis Promoted by Metal Triflates

A new synthesis of 4- and 7-carbon-substituted indoles is described. The overall sequence involves the addition of a nitrile oxide to 1 carboethoxy-2-(or 3-) allylpyrrole, hydrogenation of the intermediate isoxazoline to β-hydroxy ketone and cyclization of the ketol using magnesium or zinc triflate to the substituted indole. This new indole-forming strategy can also accommodate the introduction of oxygen functionality into the indole 6-position. Possible mechanistic aspects of the reaction are detailed.     

Viscosity and Thermal Expansion of Mixed-Alkali Borate Glasses

Transformation-range viscosity and thermal expansion measurements were made for five series (Li-Na, Li-K, Li-Cs, Na-Cs, and K-Rb) of mixed-alkali borate glasses containing 30 mol% total alkali oxide. In each case, negative deviations from additivity were observed in the isokom and glass transformation temperatures. Positive deviations from additivity were observed in the thermal expansion coefficients for the Li-Na, Li-K, and K-Rb glasses, while the Li-Cs and Na-Cs glasses exhibited negative deviations. Maximization of the deviation from additivity in the viscosity and glass transformation temperatures occurred when the radius ratio of the two alkali ions was approximately 1.7 to 1.8. Combination of the results of this study with those of earlier studies indicates that the deviations from additivity observed for these properties are independent of the identity of the glass former.     

Foam fractionation of spent sulphite liquor: Part I: Separation of surfactants

The surface activity of spent sulphite liquor (SSL) and the separation of surface active components by foam fractionation were studied. The maximum activity (lowest surface tension) of SSL was observed at a high pH. The surface tension was found to be 42 mN/m and 38 mN/m at acidic and basic pH values, respectively, and also a maximum foaminess (Σ) of 7 min was observed at pH 10. Foam fractionation reduced the surfactant concentration by 90% at an optimum pH of 10. The surfactants were concentrated in the collapsed foam as shown by the fact that the critical micelle concentrations of the unfractionated SSL and foam were 70% (v/v) and 10% (v/v), respectively. The removed surfactants were concentrated in 20% of the original liquid volume.     

A simplified method for analyzing mold filling dynamics. Part II: Extensions and comparisons with experiment

A dimensional analysis based on four parameters has been developed previously to predict injection pressure; clamp force, and bulk temperature for the injection molding of amorphous materials in center-gated disk-shaped cavities. In this paper geometric and semicrystalline-materials approximations are introduced and tested for extending the previous analysis to include multigated thin cavities and semicrystalline materials. The combination of these approximations and the previous analysis, known hereafter as the Radial Flow Method (RFM), greatly simplifies the analysis of mold filling. The geometric approximation, which is based on a simple model for the axial stress distribution in the cavity, is shown to give reasonable predictions when compared with experimental data and a numerical two-directional flow simulation for the filling of an off-center-gated rectangular cavity with acrylonitrilebutadiene-styrene copolymer (ABS). The semicrystallinematerials approximation, in which heat capacity and viscosity changes during crystallization are neglected, is shown to give good agreement with experimental data for the filling of a center-gated disk-shaped cavity with polypropylene. As an illustration, the Radial Flow Method is used to analyze the molding of a large, thin-wall automobile interior trim panel. The inlet melt temperature, mold-wall temperature, part thickness, injection rate, viscosity and gate locations are varied in a series of calculations to determine the relative effectiveness of these variables in lowering the injection pressure and Clamp force. The results obtained with the Radial Flow Method are in good agreement with those obtained by a finiteelement simulation of two-directional flow.     

Apparatus and procedure for measuring release rates from formulations of lepidopteran semiochemicals

An apparatus was developed wherein a vacuum source was used to pull air across a controlled-release-formulation dispenser or a planchet containing a known quantity of a semiochemical and into a collector filled with a polymeric adsorbent. After a set time, the semiochemical was eluted with solvent and was quantified by gas-liquid chromatography (GLC). High percentages of known quantities of the lepidopteran semiochemicals (Z)-7-dodecen-l -ol acetate (Z7DDA), boiling point (bp) 275 ° C/1 atm, (Z)-9-tetradecen-1-ol formate (Z9TDF), bp 289 °C/1 atm, and (Z,Z)-3,13-octadecadien-1-ol acetate (ZZODDA), bp 490 °C/1 atm, were recovered. The semiochemicals did not oxidize and were recovered quantitatively from the adsorbent. The release rates of Z9TDF from a controlled-release dispenser were found to be directly proportional to the airflow rates. Release rate measurements on the Z9TDF dispensers were made for the purpose of estimating the method's precision. The method was shown to give internally consistent results by measurements on another Z9TDF formulation. The accuracy of the method is discussed.Mention of a commercial or proprietary product in this paper does not constitute an endorsement by the USDA.     

Properties of cuticular oxidases used for sex pheromone biosynthesis byHeliothis zea

Biosynthesis of the aldehydic sex pheromone components released by females ofHeliothis zea was found to be catalyzed by primary alcohol oxidases residing in the cuticle that covers the glands. Activity, as indicated by conversion of primary alcohol to aldehyde, was as high in cell-free cuticle as it was in intact pheromone glands. Studies indicated that some activity was associated with the surface of the epicuticle and could be removed, into buffer, by sonication. However, the majority of activity lies within the inner epicuticle and exo- and endocuticular layers. The oxidase was not functional in pharate pupae that did not have mature adult cuticle but became functional just prior to adult emergence. The enzyme in individual glands was saturated at alcohol concentrations above 100 n. moles. Nonionic detergents did not affect the activity of the oxidase in the cuticle but treatment with either 7 M urea or 1% SDS resulted in total loss of activity. Studies on the effect of pH indicated an optimum at 6.4; however, activity was high throughout the range of 5–9. The oxidase was functional in both dichloromethane and hexane, suggesting that this enzyme system may have applications for organic synthesis of aldehydes.     

Aqueous electrochemical intercalation of bromine into graphite fibers

For the first time, graphite fibers have been electrochemically intercalated with Br⁻ that have the same structure and properties as those intercalated from vapor phase Br₂. This was accomplished by intercalating pitch-based Thornel^® K-1100 graphite fibers at low temperature (near 0 °C) and high currents (2 A) for long times (6 h). The mechanism appears to be that Br⁻ is oxidized to aqueous Br₂ which, when sufficient local concentration builds up, intercalates the fiber. This was confirmed by intercalating K-1100 fiber in a saturated aqueous Br₂ solution without passing an electrical current. The applied voltage does apparently lower the activation energy of the reaction as evidenced by the observation that P-120 and P-100 fibers will not intercalate in aqueous Br₂ unless a voltage is applied.     

A study of the methylolation of phenol using gel permeation chromatography

Gel permeation chromatography (GPC) was used to investigate the course of the sodium hydroxide catalysed methylolation of phenol in dilute aqueous solution. At low concentrations, the initial rate of methylolation was directly proportional to the concentrations of sodium hydroxide and of formaldehyde. By computer integration of the rate equations for the methylolation of phenol, of 2-methylol phenol and of 4-methylol phenol, the experimental rate curves were simulated and optimal values for the rate constants of all the methylolation steps were obtained.     

Laser Specular Reflectance and the Optical rms Roughness of Alumina

Using laser specular reflectance, the optical rms roughnesses (σ₀'S) of 42 polycrystalline aluminas (PCA's) were determined. From these conventional experimental results, a nomogram was constructed so that single grazing angle (α) measurements could be used to predict σ₀. Subsequently, the nomogram was reassessed using five commercially important PCA's and one single-crystal sapphire (SC). The outcomes were twofold: that this nomogram was valid for PCA's over the range of 0.28 σ₀ 0.10 μm, but that the nomogram was invalid for SC sapphire. When the conventional experimental method was compared with the nomogram method at three different single-angle values, a 1:1 correspondence was observed for α= 78°, 80°, and 82°. The present noncontact method is advocated for speed and cleanliness, particularly when a quality assurance method is desired.