Olefin cis‐Dihydroxylation and Aliphatic CH Bond Oxygenation by a Dioxygen‐Derived Electrophilic Iron–Oxygen Oxidant

Many iron‐containing enzymes involve metal–oxygen oxidants to carry out O₂‐dependent transformation reactions. However, the selective oxidation of C? H and C?C bonds by biomimetic complexes using O₂ remains a major challenge in bioinspired catalysis. The reactivity of iron–oxygen oxidants generated from an Fe^II–benzilate complex of a facial N₃ ligand were thus investigated. The complex reacted with O₂ to form a nucleophilic oxidant, whereas an electrophilic oxidant, intercepted by external substrates, was generated in the presence of a Lewis acid. Based on the mechanistic studies, a nucleophilic Fe^II–hydroperoxo species is proposed to form from the benzilate complex, which undergoes heterolytic O? O bond cleavage in the presence of a Lewis acid to generate an Fe^IV–oxo–hydroxo oxidant. The electrophilic iron–oxygen oxidant selectively oxidizes sulfides to sulfoxides, alkenes to cis‐diols, and it hydroxylates the C? H bonds of alkanes, including that of cyclohexane.     

Identification of Acepromazine and Its Metabolites in Horse Plasma and Urine by LC–MS/MS and Accurate Mass Measurement

Acepromazine maleate (Sedalin^®) was administered orally to six thoroughbred horses at a dose of 0.15 mg kg⁻¹. Urine and blood samples were collected up to 412 h post-administration. Plasma and urine were hydrolysed; plasma samples were then processed using liquid–liquid extraction and urine samples using solid-phase extraction. A sensitive tandem mass spectrometric method was developed in this study, achieving a lower limit of quantification for acepromazine of 10 pg mL⁻¹ in plasma and 100 pg mL⁻¹ in urine. Acepromazine, hydroxyethylpromazine, hydroxyacepromazine, hydroxyethylpromazine sulphoxide, hydroxyethylhydroxypromazine, dihydroxyacepromazine and dihydroxyhydroxyethylpromazine were detected in the post-administration samples. The parent drug and its metabolites were identified using a combination of UPLC–MS/MS and accurate mass measurement. Separation of the structural isomers hydroxyethylpromazine sulphoxide and hydroxyethylhydroxypromazine was another significant outcome of this work and demonstrated the advantages to be gained from investing in chromatographic method development.

     

A Facile Solution-Phase Approach to Transparent and Conducting ITO Nanocrystal Assemblies

Monodisperse 11 nm indium tin oxide (ITO) nanocrystals (NCs) were synthesized by thermal decomposition of indium acetylacetonate, In(acac)(3), and tin bis(acetylacetonate)dichloride, Sn(acac)(2)Cl(2), at 270 °C in 1-octadecene with oleylamine and oleic acid as surfactants. Dispersed in hexane, these ITO NCs were spin-cast on centimeter-wide glass substrates, forming uniform ITO NC assemblies with root-mean-square roughness of 2.9 nm. The assembly thickness was controlled by ITO NC concentrations in hexane and rotation speeds of the spin coater. Via controlled thermal annealing at 300 °C for 6 h under Ar and 5% H(2), the ITO NC assemblies became conductive and transparent with the 146 nm-thick assembly showing 5.2 × 10(-3) Ω·cm (R(s) = 356 Ω/sq) resistivity and 93% transparency in the visible spectral range-the best values ever reported for ITO NC assemblies prepared from solution phase processes. The stable hexane dispersion of ITO NCs was also readily spin-cast on polyimide (T(g) ～360 °C), and the resultant ITO assembly exhibited a comparable conductivity and transparency to the assembly on a glass substrate. The reported synthesis and assembly provide a promising solution to the fabrication of transparent and conducting ITO NCs on flexible substrates for optoelectronic applications.     

Scientific Methodology and Elementary School Mathematics

Investigations provide an exciting and relevant background for the study of mathematics. In this article children's conceptions of the laws of motion, introduced by Eckstein and Shemesh (1993), are extended with an emphasis placed upon the benefits to mathematics education. The focus is on the principle that the faster an object is moving when it is dropped, the greater the distance it will travel away from the drop point. The problems faced by a class of elementary school children who focus upon this experiment are described, and the impact of these problems upon the decisions made by the class are discussed. The use of mathematics in support of this experiment, particularly concepts of probability and statistics, are discussed, as well as suggestions for alternative methods of evaluating children's performance.     

Extensions in quasilinearization techniques for optimal control

This paper presents several extensions in quasilinearization techniques for optimal control problems. Techniques are developed that facilitate the application of quasilinearization to control problems where bounds on the controls exist. Toward this end, quadratic convergence for bounded continuous control is shown. A method for extending the region over which the method converges is presented, and the theoretical advantage of the extended method is shown. The work of Long is modified to provide more accurate integration while preserving its usefulness in solving problems where the final time is free. A companion paper presents computational results.This research was supported in part by the Air Force Office of Scientific Research, Grant No. AF-AFOSR-699-67.