Total synthesis of oxidized phospholipids. 3. The (11E)-9-hydroxy-13-oxotridec-11-enoate ester of 2-lysophosphatidylcholine

A total synthesis of (11E)-9-hydroxy-13-oxotridec-11-enoate ester of 2-lysophosphatidylcholine (HOT-PC) was devised to facilitate identification of this oxidized phospholipid. A lactone, 8-(3-oxo-1H,6H-2-oxinyl)octanoic acid (1), believed to be generated through an intermediate (11E)-9-hydroxy-13-oxotridec-11-enoic acid (HOT), is produced upon autoxidation of linoleic acid. A synthesis of lactone 1 methyl ester was accomplished from HOT involving a novel trans-cis isomerization that is driven to completion by cyclization to a hemiacetal. An alternative route to this carbon skeleton was also achieved that provides the lactone 1 itself.     

Light-dependent Oxygen Consumption in Bacteriochlorophyll-Serine-treated Melanoma Tumors: On-line Determination Using a Tissue-inserted Oxygen Microsensor

Successful application of anticancer therapy, and especially photodynamic therapy (PDT) mediated by type II (PDTII) processes, depends on the oxygen content within the tumor before, during and after treatment. The high consumption of oxygen during type II PDT imposes constraints on therapy strategies. Although rates of oxygen consumption and repletion during PDTII were suggested by theoretical studies, direct measurements have not been reported. Application of a novel oxygen sensor allowed continuous and direct in situ measurements (up to a depth of 8–9 mm from the tumor surface and for several hours) of temporal variations in the oxygen partial pressure (pO₂) during PDT. Highly pigmented M2R mouse melanoma tumors implanted in CD1 nude mice were treated with bacteriochlorophyll-serine (Bchl-Ser; a new photodynamic reagent) and were subjected to fractionated illumination (700 < λ. < 900 nm) at a fluence rate of 12 mW cm^-2. This illumination led to total oxygen depletion with an average consumption rate of 7.2 uAf(O₂) s^-1. Spontaneous reoxygenation (at an average rate of 2.5 µM(O₂)/s) was observed during the following dark period. These rates are in good agreement with theoretical considerations (Foster et al., Radiat. Res. 126, 296,1991 and Henning et al, Radiat. Res. 142, 221, 1995). The observed patterns of oxygen consumption and recovery during prolonged periods of light/dark cycles were interpreted in terms of vasculature damage and sensitizer clearance. The presented data support the previously suggested advantages of fractionated illumination for type II photodynamic processes.     

Interactions Between Tetra(trifluoromethylsulfonyl)-1,4,8,11-tetraazocyclotetradecane and Perchlorate Anion in Propylene Carbonate, Nitromethane, Acetonitrile, and Tetrahydrofuran

Electrical conductance measurements are reported for lithium perchlorate andthe anion receptor tetra(trifluoromethylsulfonyl)-1,4,8,11-tetraazocyclotetradecane(TTCD) in different aprotic solvents (propylene carbonate, nitromethane,acetonitrile, and tetrahydrofuran). The data have been analyzed by a suitablemethod based on the Lee-Wheaton theory on mixed electrolytes in order to obtainthe true thermodynamic formation constants of macrocyclic-anion complexes andthe ion pairs of both the uncomplexed (ClO₄ ^–)and complexed (TTCD-ClO₄ ^–)anions. The results show that the anion-ligand formation constants increase withdecreasing dielectric constant and that the presence of the ligand increases theionization of lithium perchlorate and enhances the transference number of lithiumion. These findings are of particular interest in view of the technologicalapplication of anion receptors in electrolyte solutions for lithium batteries.     

Hyperfine interaction of 181Ta in nickel

Nuclear gamma resonance spectroscopy was used to study the hyperfine interaction of ¹⁸¹Ta impurities in nickel at room temperature and above the Curie point. Both the hyperfine field for ¹⁸¹Ta in nickel at room temperature and the isomer shift relative to Ta metal have been derived.     

Total synthesis of anhydro levug̀landin D2

Total synthesis of anhydro levuglandin D₂ [9-acetyl-8-formyl-5(Z),9(E),11(E)-hepta-decatrienoic acid] confirms the structure assigned to this 9,10-seco prostanoic acid product from solvent induced rearrangement of the prostaglandin endoperoxide PGH₂ in aqueous solution.