Photochemistry of trans-Cr(cyclam)(ONO)2+, a nitric oxide precursor.

Experimental and density functional theory (DFT) studies are described that are focused on outlining the reactivity of the known photochemical nitric oxide precursor trans-Cr(cyclam)(ONO)(2)(+) ("CrONO", cyclam = 1,4,8,11-tetrazacycltetradecane). Studies in both aerated and deaerated aqueous media are described as are the roles of both the oxidant O(2) and a reductant such as glutathione in trapping the apparent Cr(IV) photoreaction intermediate trans-Cr(cyclam)(O)(ONO)(+). Also reported and characterized structurally is the Cr(V) product of long-term photolysis in the absence of reducing agents, the trans-dioxo species [trans-Cr(cyclam)(O)(2)](ClO(4)).

Identification of hydroxy fatty acids by liquid chromatography-atmospheric pressure chemical ionization mass spectroscopy in Euglena gracilis.

Hydroxy fatty acids from Euglena gracilis were identified by reverse-phase high performance liquid chromatography coupled to a mass spectrometer run in atmospheric pressure chemical ionization positive ion mode. These metabolites were converted to methyl esters to improve stability and chromatographic properties. A detection limit of 20 pg/microl per injection was determined for 5-HETE methyl ester based on the signal to noise ratio of the m/z 317 ion which corresponds to the loss of a hydroxyl group (M-17) and the major fragment in all HETE methyl esters studied.

Reactivity of Enol Carbonates with Ozone.

Several dienes of varying steric bulk containing an enol carbonate have been synthesized and reacted selectively with ozone at the isolated double bonds. Rate measurements have been made for ozonolysis in a series of substituted cyclohexenes to demonstrate the unusually slow reactivity of the enol carbonate. Proton and carbon NMR chemical shifts have been presented to show that the enol carbonate is not particularly electron deficient in its double bond.