An expeditious construction of 9-membered rings

9-Membered rings are readily constructed through a radical addition-cyclisation sequence on a 1,6-dien-3-ol system followed by a Grob-type fragmentation.     

Chromium(VI) oxide oxidation of non‐ethoxylated and ethoxylated alcohols for determination by electrospray ionization mass spectrometry

A new derivatization procedure to increase the sensitivity of electrospray ionization mass spectrometry (ESI‐MS) to non‐ethoxylated and ethoxylated alcohols was investigated. The analytes were oxidized with chromium(VI) oxide and the resulting carboxylic and ethoxy‐carboxylic acids were isolated by extraction with ethyl acetate; the extracts were alkalinized and infused into the ESI‐MS system working in the negative‐ion mode. The yields of the combined oxidation‐extraction were ca. 100% for non‐ethoxylated fatty alcohols dissolved in acetone and they decreased moderately in samples containing increasing amounts of water (e.g., a 75% yield was obtained with 50% water). Ethoxylated alcohols with more than two ethylene oxide units resulted in yields of ca. 60%. Low limits of detection (LODs) were obtained when the procedure was applied to the analysis of body‐care products and cosmetics containing fatty alcohols, e.g., in a varicose‐vein cream, the LODs were 25 µg cetyl alcohol and 7.5 µg stearyl alcohol (detected as palmitic acid and stearic acid, respectively) per gram of sample. High molecular mass alcohols were also detected in seawater after pre‐concentration by solid‐phase extraction. Thus, the proposed method is particularly valuable for use in industrial samples having complex matrices and in environmental samples and it is competitive with other methods for the analysis of trace amounts of fatty alcohols. Copyright © 2010 John Wiley & Sons, Ltd.     

ior egf/r3: A murine monoclonal antibody for diagnostic of epithelial tumors

Monoclonal antibody ior egf/r3 is a IgG2a, recognizes the epidermal growth factor receptor. The aim of the present work was to evaluate the diagnostic efficacy of the^99mTc-labeled ior egf/r3 for the detection of epithelial tumors, its metastasis and its recurrences. The sensitivity by organs was: brain 100%, diegestive tract 90%, head and neck 89%, lung 84% and breast 79%. The overall sensitivity, specificity, accuracy, positive predictive value and negative predictive value of the immunoscintigraphic imaging were 84.1%, 100%, 86.5%, 100% and 52.4%, respectively. Immunoscintigraphy with^99mTc-ior egf/r3 is useful for the diagnosis and follow-up of epithelial tumors.     

Delimitation of service areas in reverse logistics networks with multiple depots

This paper describes a heuristic approach for the definition of service (or influence) areas of multiple depots in a reverse logistics network. This work is based on a case study: the recyclable waste collection system with 5 depots that covers seven municipalities in the Alentejo region, southern Portugal. The system optimization considers two objectives, related with economic and organizational issues: minimizing the variable costs (function of the travelled distances by the collection vehicles), and the pursuit of equity, aiming at minimizing the workload differences among depots. The goal of balancing workloads poses a problem not usually treated in the existing literature. This fact required the development of a new approach with innovative elements adjusted to the existing circumstances.     

Niobium oxide solid catalyst: esterification of fatty acids and modeling for biodiesel production

Biodiesel can be obtained from fatty acid raw materials through esterification. The reactivity of lauric, palmitic, stearic, oleic, and linoleic fatty acids with methanol using powdered niobic acid as a heterogeneous catalyst was investigated in this work, both experimentally (in a batch reactor) and theoretically. A 2³ experimental design was used, with methanol/fatty acid molar ratio, catalyst concentration, and temperature as main factors. An empirical model demonstrated that temperature is the most important variable. Fourteen heterogeneous and 56 homogeneous‐like kinetic models were tested. A homogeneous‐like model considering zero order for all species and inhibition by water was the most adequate for experiments without catalyst. A homogeneous‐like model considering a second‐order reaction in relation to the fatty acid and no water inhibition was the most adequate for niobic acid catalyzed reaction. Molecular modeling confirmed the experimental results showing that the reactivity is directly related to the increase of unsaturated bonds and the reduction of carbon chain length. The polarity of the fatty acid is determinant in the reactivity. At the molecular level, reaction occurs between the HOMO orbital of methanol and LUMO orbitals of fatty acids and reactivity is higher when the energy difference between these orbitals is lower. Copyright © 2010 John Wiley & Sons, Ltd.     

Density functional study for the polymerization of ethylene monomer using a new nickel catalyst

The present computational study was designed to study the polymerization of ethylene catalyzed by a new Ni‐based PymNox organometallic compound. Recently, we have synthesized and tested the behavior of this type of catalyst in olefin polymerization. It has been experimentally observed that the unsubstituted catalyst Ni2 (aldimino PymNox catalyst ) is less active than the methyl substituted Ni1 (acetaldimino PymNox catalyst ) analogue. The reactivity of both catalysts was examined using density functional theory (DFT) models. Our results indicate that the methyl substituted Ni1 introduces some additional steric hindrance that probably renders a more suitable catalyst conformation for the monomer incorporation. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1160–1165, 2010     

Gamma coloration of mixed crystals of KCl–KBr doped with Pb

The amount of the first stage coloration in KCl_1−xBr_x doped with Pb²⁺ has been investigated as a function of the dose rate and impurity concentration. For a dose rate of 12.88 kGy/h, the F color center production was independent of the quantity of Pb²⁺, and varied according to the ratio KCl/KBr. At a proportion of 50% of each halogen the typical stages were observed. However, if the dose rate is less than 3.22 kGy/h, the coloration production depends on the quantity of Pb²⁺.