RESUMEN
There is great practical and scholarly interest in the identification of pigments in works of art. This paper compares the effectiveness of the widely used Raman Spectroscopy (RS), with hyperspectral imaging (HSI), a reflectance imaging technique, to evaluate the reliability of HSI for the identification of pigments in historic works of art and to ascertain if there are any benefits from using HSI or a combination of both. We undertook a case study based on six Armenian illuminated manuscripts (eleventh-eighteenth centuries CE) in the Bodleian Library, University of Oxford. RS, and HSI (380-1000 nm) were both used to analyse the same 10 folios, with the data then used to test the accuracy and efficiency of HSI against the known results from RS using reflectance spectra reference databases compiled by us for the project. HSI over the wavelength range 380-1000 nm agreed with RS at best 93% of the time, and performance was enhanced using the SFF algorithm and by using a database with many similarities to the articles under analysis. HSI is significantly quicker at scanning large areas, and can be used alongside RS to identify and map large areas of pigment more efficiently than RS alone. HSI therefore has potential for improving the speed of pigment identification across manuscript folios and artwork but must be used in conjunction with a technique such as RS.
RESUMEN
"Amplified" electron transfer is observed purely based on electron transfer kinetic effects at modified carbon surfaces. An anodic attachment methodology is employed to modify the surface of glassy carbon or boron doped diamond electrodes with poly-ethylene glycols (PEGs) for polymerisation degrees of n = 4.5 to 9.1 (PEG200 to PEG400). Voltammetry and impedance data for aqueous Fe(CN)6(3-/4-) suggest systematic PEG structure-dependent effects on the standard rate constant for heterogeneous electron transfer as a function of PEG deposition conditions and average polymer chain length. Tunnel distance coefficients are polymerisation degree dependent and estimated for shorter PEG chains, ß = 0.17 Å(-1) for aqueous Fe(CN)6(3-/4-), consistent with a diffuse water-PEG interface. In contrast, electron transfer to 1,1'-ferrocene-dimethanol (at 1 mM concentration) appears un-impeded by PEG grafts. Mediated or "amplified" electron transfer to Fe(CN)6(3-/4-) based on the 1,1'-ferrocene-dimethanol redox shuttle is observed for both oxidation and reduction with estimated bimolecular rate constants for homogeneous electron transfer of kforward = 4 × 10(5) mol dm(3) s(-1) and kbackward = 1 × 10(5) mol dm(3) s(-1). Digital simulation analysis suggests an additional resistive component within the PEG graft double layer.