Long-term particulate matter (PM) chemical composition measurements were performed in Cyprus at two different sites (an urban/traffic site (“LIMTRA”) and a remote/background site (“AGM”)) in an effort to assess (i) the spatial and temporal variability of fine (PM2.5) particulate matter in the eastern Mediterranean; (ii) the main sources contributing to their levels and their relationship with the characteristics of the sampling location; and (iii) the enhancement effect of local anthropogenic and natural biogenic sources on PM levels. To this end, the simultaneous determination of 118 individual Secondary Organic Aerosol (SOA) components (carboxylic acids, organosulfates, and organonitrates) was performed. The “AGM” station showed average SOA yields more than three times higher than those at the “LIMTRA” station (15 ng∙m−3 and 4.4 ng∙m−3, respectively), whilst the organonitrate levels were higher at “LIMTRA” than at “AGM” (3.3 ng∙m−3 and 1.8 ng∙m−3, respectively). The most abundant SOA species were hydroxy-acetone sulfate, glycolic acid sulfate, and lactic acid sulfate (21 ng∙m−3 at “LIMTRA” and 84 ng∙m−3 at “AGM”). The highest SOA load was observed in spring at “AGM” (18 ng∙m−3) and in summer at “LIMTRA” (6.8 ng∙m−3). Two statistical factorization tools, Principal Component Analysis and Positive Matrix Factorization, were applied to extract common patterns and point to possible SOA sources and SOA formation pathways; the different categorization approaches produced similar results.
The synthesis of a small library of fused Cyclic Aryl Amino Carbon (f-CArAC) carbene precursors in the form of 1,1,2,4-tetraaryl-1H-isoindol-2-ium triflate (6), (7-R) (R = tBu, CF3) or 3,3-dimethyl-2,8-bis-arene-substituted-3,4-dihydro-isoquinolin-2-ium hydrogen-dichloride (8) and 2,4,8-tri(substituted)-isoquinolin-2-ium tosylate salts (12) has been achieved. All of them feature an arene incorporated on the annulated benzene ring of the corresponding heterocycle, introduced at the early stages of their synthesis via the Suzuki cross-coupling reaction between 2,6-dibromo-benzaldehyde and the desired aryl boronic acid. The terphenyl-2′carbaldehyde by-products of this Suzuki reaction are useful starting points for the preparation of two new iminium iodide salts (10-R) (R = H, CF3) as potential precursors to access ACyclic Amino Carbon (ACAC) carbenes. Compounds (6) and (7-tBu) react readily with hydroxide either in THF or in a biphasic Et2O/aqueous OH− solution to produce the substituted isoindolinols (13) and (14), respectively. The thermal dehydration of the former generates the corresponding f-CArAC carbene in situ, which is trapped by Cu(I)Cl furnishing, a rare example of a two-coordinate Cu(I) complex (15) supported by this new ligand scaffold.