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Durham e-Theses
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Interactions of fluorophores with complex surfaces and spectroscopic examinations of ancient manuscripts

DUCKWORTH, ANDREW,ROBERT (2017) Interactions of fluorophores with complex surfaces and spectroscopic examinations of ancient manuscripts. Doctoral thesis, Durham University.

PDF - Accepted Version
[img]Archive (ZIP) (Zip archive of two folders, content specified in thesis appendices. Formats include MATLAB figures.) - Supplemental Material


In the first part of this thesis, it was found by fibre-optic fluorescence spectroscopy, that the greening of fabrics washed in optical brighteners is due to a reabsorption effect. The quantum yield of fluorescence of the optical brighteners OB15, OB36 and OB49 in water are $ 0.11 $, $ 0.08 $ and $ 0.71 $ respectively. Their respective fluorescence natural lifetimes are $ 6700\pm109 $, $ 5971\pm712 $ and $ 1685\pm22 $ ps. In solution, the excited state of OB15 experiences more competing relaxation processes as the solvatochromic shift increases. OB49 displays the opposite trend.

A literature cellulose model surface is employed as a cotton mimic for evanescent wave fluorescence studies. Two model greases are similarly developed and used, and a third is presented for future work. These are based on surface-specific reactions with glass substrates, and the doping of a regenerated cellulose film with long chain alcohols. On doped cellulose surfaces, some low quantum yields occur compared to clean cellulose and bulk solution. Photobleaching behaviours are also observed. Both dyes physisorb rigidly to cellulose and grease models.

The second part of this thesis identifies the pigment palette of the earliest Northumbrian manuscripts pre- and post-1066, by Raman and diffuse reflectance spectroscopy. It develops a suite of multispectral imaging programs in MATLAB for facile classification of pigments across a page ab initio, using data reduction and colour spaces.

Raman and reflectance data are meta-analysed using symmetric permutation to split manuscripts and pigments into groups ab initio. It was also generalised, that the palette of the pre-Hastings selected manuscripts contained vergaut, indigo, orpiment, impure red lead, and copper green pigments, as well as orcein purples. Immediately post-1066 white lead, red ochre, vermilion and lapis lazuli appear in the palette in England, though vergaut and indigo disappear and the red lead used is essentially pure.

Item Type:Thesis (Doctoral)
Award:Doctor of Philosophy
Keywords:spectroscopy;manuscripts;fluorescence;tcspc;anisotropy;Raman;pigments;fabric;evanescent wave;surface;interface
Faculty and Department:Faculty of Science > Chemistry, Department of
Thesis Date:2017
Copyright:Copyright of this thesis is held by the author
Deposited On:26 Sep 2017 10:57

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