A molecular study of modern oil paintings: investigating the role of dicarboxylic acids in the water sensitivity of modern oil paints.

The 20th century has seen a significant evolution in artists' paint formulation and technology which is likely to relate to the new conservation challenges frequently presented by modern oil paintings, including unpredictable water- and solvent-sensitivity. This study examined the molecular causes and mechanisms behind these types of modern oil paint vulnerability. Research performed up to now has suggested a correlation between the occurrence of water sensitivity and the presence of relatively high amounts of extractable free dicarboxylic acids. To explore this further, as well as the influence of paint formulation, a set of model paint samples, produced in 2006 using commercial tube paints to which known amounts of additives were added, were analysed. The samples were tested for water sensitivity by aqueous swabbing and characterised using transmission Fourier Transform-Infra Red spectroscopy (FTIR) to determine the molecular composition of the main paint constituents, High Performance Liquid Chromatography-Mass Spectrometry (HPLC-MS), to identify the type(s) of drying oils used as binders, and Gas Chromatography-Mass Spectrometry (GC-MS) using a recently developed analytical procedure that can discriminate and quantify free fatty and dicarboxylic acids, as well as their corresponding metal soaps (carboxylates of fatty and dicarboxylic acids). The results indicated that the addition of small amounts of additives can influence the water sensitivity of an oil paint, as well as its molecular composition. Additionally the nature of the ionomeric/polymeric network appears to be a significant determining factor in the development of water sensitivity.

Stereoselective synthesis of chiral 3-aryl-1-alkynes from bromoallenes and heterocuprates.

The synthesis of chiral 3-aryl-1-alkynes 3 via cross-coupling of 3-alkyl- and 3,3-dialkyl-1-bromo-1,2-dienes 1 and arylbromocuprates (RCuBr)MgBr.LiBr 2 was examined. With phenylcopper reagents and its para-substituted derivatives, as well as with 2-naphthyl cuprates, the reaction gave compounds 3 with high regioselectivity and good yields on the chemically pure product. On the contrary, when ortho-substituted phenyl reagents and 1-naphthyl cuprates were used, the regioselectivity of the process was very dependent upon the steric requirements of the alkyl substituents on the bromoallenic substrate. When the steric bulk was increased, remarkable quantities of isomeric arylallenes 4 were also observed in the reaction mixtures. The high 1,3-anti stereoselectivity of the coupling process allowed us to obtain enantiomerically enriched 3-aryl-1-alkynes from optically active allenic substrates, thus indicating a simple pathway toward the synthesis of quaternary stereogenic centers characterized by an aryl group. A possible cross-coupling mechanism was also suggested to explain the regio- and stereochemical data. For the preparation of omega-functionalized 3-phenyl-1-alkynes, the reaction of 1-bromo-3-phenylpropadiene with Knochel reagents RCu(CN)ZnCl.2LiCl was also studied; this reaction led to the acetylenic compounds in high yields mainly when the R group (also omega-functionalized) on the copper reagent was primary.

Mechanistic studies on the asymmetric alkylation of amino ester enolates using a copper(II)salen catalyst.

Hammett data indicate that the asymmetric alkylation of enolates catalysed by copper(II)salen complex 1, proceeds by an asynchronous S(N)2 reaction and that the role of the catalyst is to enhance the nucleophilicity of the enolate.