Performance evaluation of mapping and linear imaging FTIR microspectroscopy for the characterisation of paint cross sections.

Different Fourier transform infrared microspectroscopic techniques, using attenuated total reflection (ATR) mode and single-element mercury-cadmium-telluride (MCT) detector (mapping) or multielement MCT detector (raster scanning), are compared with each other for the characterisation of inorganic compounds and organic substances in paint cross sections. All measurements have been performed on paint cross sections embedded in potassium bromide, a transparent salt in the mid-infrared region, in order to better identify the organic materials without the interference of the usual embedding resin. The limitations and advantages of the different techniques are presented in terms of spatial resolution, data quality and chemical information achieved. For all techniques, the chemical information obtained is found to be nearly identical. However, ATR mapping performed with a recently developed instrumentation shows the best results in terms of spectral quality and spatial resolution. In fact, thin organic layers (approximately 10 microm) have been not only identified but also accurately located. This paper also highlights the recent introduction of multielement detectors, which may represent a good compromise between mapping and imaging systems.

Selective generation and reactivity of 5'-adenosinyl and 2'-adenosinyl radicals.

The reaction of hydrated electrons (e(-)(aq) with 8-bromoadenosine 7 has been investigated by radiolytic methods coupled with product studies. Pulse radiolysis revealed that one-electron reductive cleavage of the C-Br bond gives the C8 radical 8 followed by a fast radical translocation to the sugar moiety. The reaction is partitioned between C5' and C2' positions in a 60:40 ratio leading to 5'-adenosinyl radical 9 and 2'-adenosinyl radical 11. This radical translocation from C8 to different sites of the sugar moiety has also been addressed computationally by means of DFT B3LYP calculations. In addition, ketone 21 was prepared and photolyzed providing an independent generation of C2' radical 11. Both C5' and C2' radicals undergo unimolecular reactions. Radical 9 attacks adenine with a rate constant of 1.0 x 10(4) s(-1) and gives the aromatic aminyl radical 10, whereas C2' radical 11 liberates adenine with a rate constant of 1.1 x 10(5) s(-1).